JPH0718457A - Separation agent at annealing for grain oriented silicon steel sheet - Google Patents
Separation agent at annealing for grain oriented silicon steel sheetInfo
- Publication number
- JPH0718457A JPH0718457A JP16365993A JP16365993A JPH0718457A JP H0718457 A JPH0718457 A JP H0718457A JP 16365993 A JP16365993 A JP 16365993A JP 16365993 A JP16365993 A JP 16365993A JP H0718457 A JPH0718457 A JP H0718457A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- annealing
- alumina
- oriented silicon
- silicon steel
- 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.)
- Pending
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- Manufacturing Of Steel Electrode Plates (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は方向性珪素鋼板の仕上げ
焼鈍の際に用いられる焼鈍分離剤に関するものである。
本焼鈍分離剤を用いることにより、グラス皮膜を生成さ
せないことによる打ち抜き性の良好な方向性珪素鋼板、
あるいは鏡面を有する極めて鉄損の低い方向性珪素鋼板
が製造できる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an annealing separator used in finish annealing of grain-oriented silicon steel sheet.
By using the main annealing separator, a grain-oriented silicon steel sheet having good punchability by not forming a glass film,
Alternatively, a grain-oriented silicon steel sheet having a mirror surface and extremely low iron loss can be manufactured.
【０００２】[0002]
【従来の技術】方向性珪素鋼板の一般的な製造方法は以
下の通りである。Ｓｉを４％以下含有する珪素鋼スラブ
を熱延し、１回もしくは中間焼鈍を挟む２回の冷延によ
り最終板厚に仕上げ、湿潤雰囲気中の焼鈍により脱炭と
ＳｉＯ2 を主体とするサブスケールを形成させる。続い
てＭｇＯを主体とする焼鈍分離剤を水に懸濁してスラリ
ー状にして塗布、乾燥の後コイルに巻き取り、高温仕上
げ焼鈍を行う。この高温仕上げ焼鈍により、鋼板中にお
いてはゴス方位の二次再結晶粒が発達し、一方鋼板表面
においては焼鈍分離剤中のＭｇＯとサブスケール中のＳ
ｉＯ2 が反応して、フォルステライトを主体とするグラ
ス皮膜が形成される。仕上げ焼鈍後の方向性珪素鋼板に
は必要に応じて絶縁コーティングが施される。2. Description of the Related Art A general method for manufacturing a grain-oriented silicon steel sheet is as follows. A silicon steel slab containing 4% or less of Si is hot-rolled and cold-rolled once or twice with an intermediate anneal to finish the final thickness, and decarburization and SiO 2 -based sub-annealing is performed by annealing in a wet atmosphere. Allow the scale to form. Subsequently, an annealing separator containing MgO as a main component is suspended in water to form a slurry, which is applied, dried, and then wound on a coil and subjected to high temperature finish annealing. By this high-temperature finish annealing, secondary recrystallized grains of Goss orientation develop in the steel sheet, while on the surface of the steel sheet, MgO in the annealing separator and S in the subscale are developed.
iO 2 reacts to form a glass film mainly composed of forsterite. An insulating coating is applied to the grain-oriented silicon steel sheet after finish annealing as needed.
【０００３】方向性珪素鋼板の用途は主に発電機、変圧
器等の鉄芯材である。鉄芯は、金型による打ち抜きもし
くは剪断によって所定形状に加工された方向性珪素鋼板
の積層によって製造される。打ち抜きの際に問題となる
のは返りである。返りが大きくなると鉄芯積層体におい
て端面短絡が起こり、鉄損の異常増加が起こる。現行の
方向性珪素鋼板の表面には前述のように、フォルステラ
イトを主体とするグラス皮膜が形成されているが、この
皮膜は硬質である。したがって、打ち抜きのための金型
の摩耗が激しく、打ち抜き返りを防止するためには金型
の再研磨あるいは交換を頻繁に行わなければならない。
これは作業性を著しく低下させ、またコストの上昇をま
ねく。The grain oriented silicon steel sheet is mainly used as an iron core material for generators, transformers and the like. The iron core is manufactured by stacking grain-oriented silicon steel plates that are processed into a predetermined shape by punching or shearing with a die. It is the return that is a problem when punching. When the return is large, an end face short circuit occurs in the iron core laminated body and an abnormal increase in iron loss occurs. As described above, the glass film mainly composed of forsterite is formed on the surface of the current grain-oriented silicon steel sheet, but this film is hard. Therefore, the die for punching is heavily worn, and the die must be frequently re-polished or replaced in order to prevent punching back.
This significantly lowers the workability and increases the cost.
【０００４】一方、鉄芯材の磁気的特性として要求され
る項目の中で最も重要なものは鉄損である。鉄損が低い
ほど発電機、変圧器等に使用された場合の変換ロスが減
少するからである。方向性珪素鋼板の鉄損値を低減させ
る手段としては、鋼板板厚の減少、鋼中Ｓｉ含有量の増
加、鋼板の高磁束密度化、皮膜による鋼板への張力付与
等が検討されてきた。最近では鋼板に線状の歪や溝を導
入する、磁区制御技術も開発されている。これらの鉄損
低減技術は工業的にはほぼ完成されたと言って良く、さ
らなる低鉄損化を図るためには新しい手段を開発する必
要がある。On the other hand, the most important item required as the magnetic characteristics of the iron core material is iron loss. This is because the lower the iron loss, the smaller the conversion loss when used in a generator, transformer, etc. As means for reducing the iron loss value of the grain-oriented silicon steel sheet, reduction of the steel sheet thickness, increase of Si content in the steel, increase of magnetic flux density of the steel sheet, application of tension to the steel sheet by coating, etc. have been studied. Recently, magnetic domain control technology has been developed that introduces linear strains and grooves into the steel sheet. It can be said that these iron loss reduction technologies have been almost completed industrially, and it is necessary to develop new means in order to further reduce the iron loss.
【０００５】最近注目されている課題は、鋼板と皮膜界
面の平坦化である。現行の方向性珪素鋼板においてはグ
ラス皮膜と鋼板との界面の凹凸が激しく、磁化過程にお
ける磁壁移動を阻害している。したがってグラス皮膜の
ない方向性珪素鋼板を製造できるならば、さらなる低鉄
損化が図れる。[0005] Recently, a subject that has attracted attention is the flattening of the interface between the steel sheet and the coating. In the current grain-oriented silicon steel sheet, the interface between the glass film and the steel sheet is severely uneven, which hinders domain wall movement during the magnetization process. Therefore, if a grain-oriented silicon steel sheet without a glass coating can be manufactured, further reduction in iron loss can be achieved.
【０００６】一旦形成されたグラス皮膜を酸洗で除去す
る方法は良く知られている。しかしながら、フォルステ
ライトは化学的に安定な化合物であり、比較的濃度の高
くかつ温度の高い酸洗液に長時間浸漬しなければならな
い。したがって、工業的な規模で酸洗を行うことは設備
的にもコスト的にも困難が伴う。A method of removing a glass film once formed by pickling is well known. However, forsterite is a chemically stable compound and must be soaked for a long time in a relatively concentrated and high temperature pickling solution. Therefore, it is difficult to perform pickling on an industrial scale in terms of equipment and cost.
【０００７】仕上げ焼鈍後に酸洗する方法に替わって検
討されてきた方法は、不活性な焼鈍分離剤を用いる方法
である。例えば、米国特許３，７８５，８８２において
は粗粒高純度アルミナを用いてグラス皮膜形成を防止す
る方法が開示されている。しかしながら、粗粒アルミナ
はスラリーになりにくくかつ、塗布乾燥後の鋼板に対す
る付着性が極めて弱い。したがって仕上げ焼鈍中に鋼板
間の焼き付きが起こって安定な製造が行えない。A method that has been examined in place of the method of pickling after finish annealing is a method of using an inert annealing separating agent. For example, U.S. Pat. No. 3,785,882 discloses a method of using coarse-grained high-purity alumina to prevent glass film formation. However, coarse-grained alumina is unlikely to be a slurry, and its adhesion to the steel sheet after coating and drying is extremely weak. Therefore, seizure occurs between the steel sheets during the finish annealing, and stable manufacturing cannot be performed.
【０００８】一方、１μｍ未満の微粒アルミナは水に懸
濁すると容易にスラリーになり、かつ塗布乾燥後の鋼板
に対する密着性も良好であるが、高価である。さらに微
粉アルミナによるスラリーを焼鈍分離剤として用いた場
合には、しばしば仕上げ焼鈍時にアルミナの鋼板への焼
き付きが起こる。このような問題に対し、特開昭５３−
２２４４３号および特開昭５５−８９４２３号公報にお
いては、微細アルミナ焼鈍分離剤の焼き付きを防止する
ために含水珪酸塩を添加する方法が開示されている。On the other hand, fine alumina particles of less than 1 μm easily become a slurry when suspended in water, and have good adhesion to a steel sheet after coating and drying, but they are expensive. Furthermore, when a slurry of fine alumina is used as an annealing separator, seizure of alumina on the steel sheet often occurs during finish annealing. To solve such a problem, Japanese Patent Laid-Open No. 53-
No. 22443 and Japanese Patent Laid-Open No. 55-89423 disclose a method of adding a hydrous silicate to prevent seizure of a fine alumina annealing separator.
【０００９】また、仕上げ焼鈍時の鈍化（鋼板中の不純
物元素の焼鈍分離剤への吸い上げ）を促進するためにア
ルミナに不活性ＭｇＯ、Ｃａ化合物やＳｒ化合物を添加
する方法が、特開昭５９−９６２７８号、同６４−７９
３８１号、特開平３−２３８０号公報に開示されてい
る。しかしながら、これらの添加物はいずれもわずかな
がら水和性があり、アルミナの焼き付きを完全には防止
できない。Further, a method of adding an inert MgO, Ca compound or Sr compound to alumina in order to accelerate the blunting during the finish annealing (sucking up the impurity element in the steel sheet to the annealing separator) is disclosed in JP-A-59 / 59. -96278, 64-64
No. 381 and JP-A-3-2380. However, all of these additives are slightly hydratable and cannot completely prevent the seizure of alumina.
【００１０】さらに、特願平５−０４３８１０号におい
ては、脱炭焼鈍後に脱炭酸化膜を除去した後、アルミナ
等の不活性焼鈍分離剤を塗布して仕上げ焼鈍を行う方向
性珪素鋼板の製造方法が提起されている。すなわち、脱
炭酸化膜の除去により鋼板表面直下の介在物の生成が防
止でき、酸化膜を除去しなかった場合に比較して鉄損値
（Ｗ17/50 ）が０．１w/kg程度低い方向性珪素鋼板が得
られるとされている。この技術を工業的に行うにあたっ
ても、焼き付きがなくかつ鋼板に対する付着性の良好な
焼鈍分離剤が必要である。Further, in Japanese Patent Application No. 5-043810, production of a grain-oriented silicon steel sheet in which a decarbonation film is removed after decarburization annealing, and then an inert annealing separating agent such as alumina is applied for finish annealing. The method has been raised. That is, the removal of the decarboxylation film can prevent the formation of inclusions just below the surface of the steel sheet, and the iron loss value (W 17/50 ) is about 0.1 w / kg lower than when the oxide film is not removed. It is said that a grain-oriented silicon steel sheet can be obtained. Even when this technique is applied industrially, an annealing separator that does not seize and has good adhesion to steel plates is required.
【００１１】[0011]
【発明が解決しようとする課題】本発明は最終仕上げ焼
鈍後に皮膜形成や焼鈍分離剤の焼き付きのない、したが
って打ち抜き性、磁気特性の良好な方向性珪素鋼板を得
るための焼鈍分離剤を提供しようとするものである。The present invention provides an annealing separator for obtaining a grain-oriented silicon steel sheet having no film formation and no seizure of the annealing separator after the final finish annealing, and therefore has good punchability and magnetic properties. It is what
【００１２】[0012]
【課題を解決するための手段】発明者らは、まず、実際
の方向性珪素鋼板の焼鈍分離剤塗布工程における操業性
に対するアルミナの平均粒径依存性について調査した。
アルミナの平均粒径はマイクロトラックにより粒度分布
を測定し、累積重量百分率において５０％に相当する粒
径から見積もった。その結果以下のことが判明した。[Means for Solving the Problems] First, the inventors investigated the dependence of the average grain size of alumina on the operability in the actual step of applying an annealing separator to a grain-oriented silicon steel sheet.
The average particle size of the alumina was estimated by measuring the particle size distribution by Microtrac and calculating the particle size corresponding to 50% in cumulative weight percentage. As a result, the following was revealed.
【００１３】平均粒径１μｍ未満のアルミナを用いた場
合には焼鈍分離剤塗布工程において全く問題がない。１
〜２０μｍの場合にはスラリー作製は可能であるが、ス
ラリー塗布乾燥後の鋼板に対する付着性が悪く、コイル
の巻き取りや搬送の際に焼鈍分離剤が剥離してしまう。
２０μｍを超えると沈降しやすくスラリーが作製しにく
い。When alumina having an average particle size of less than 1 μm is used, there is no problem in the annealing separator application process. 1
When the thickness is up to 20 μm, the slurry can be prepared, but the adhesion to the steel plate after the slurry is applied and dried is poor, and the annealing separator is peeled off when the coil is wound or conveyed.
If it exceeds 20 μm, it is likely to settle and it is difficult to prepare a slurry.
【００１４】次に、仕上げ焼鈍後の焼鈍分離剤の鋼板に
対する焼き付き性のアルミナ粒径依存性について調査し
た。アルミナの焼き付きの度合いは仕上げ焼鈍後の酸素
量によって評価した。表１に示したように、平均粒径１
μｍ未満のアルミナからなるスラリーを塗布した場合に
はアルミナの焼き付きが起こる。これは、粒径が細かく
なると表面積が増大し、アルミナ粒子が活性化して焼結
しやすくなることが原因であると思われる。Next, the dependence of the seizure property of the annealing separator after finish annealing on the steel sheet on the alumina particle size was investigated. The degree of seizure of alumina was evaluated by the amount of oxygen after finish annealing. As shown in Table 1, average particle size 1
When a slurry made of alumina having a particle size of less than μm is applied, the seizure of alumina occurs. It is considered that this is because when the particle size becomes fine, the surface area increases, and the alumina particles are activated and easily sintered.
【００１５】[0015]
【表１】 [Table 1]
【００１６】以上の調査から、焼鈍分離剤として操業性
の良い細粒アルミナを用いた場合にはアルミナの鋼板へ
の焼き付きが発生し、焼き付きのない粗粒アルミナを用
いた場合には操業性が悪いことが判明した。そこで粗粒
アルミナと細粒アルミナを混合して用いるならば、スラ
リー塗布乾燥後の焼鈍分離剤の鋼板に対する付着性を改
善できるのではないかと考えた。From the above investigation, when fine-grained alumina having good operability as an annealing separator is used, seizure of alumina occurs on the steel sheet, and when coarse-grained alumina having no seizure is used, operability is deteriorated. It turned out to be bad. Therefore, it was thought that if a mixture of coarse-grained alumina and fine-grained alumina is used, the adhesion of the annealing separator after slurry coating and drying to the steel sheet can be improved.
【００１７】図１は平均粒径１〜５０μｍの各種アルミ
ナ粉に１μｍ未満の微粉アルミナを混合してスラリーを
作製し、方向性珪素鋼板の焼鈍分離剤の塗布工程におけ
る操業性について評価した結果である。○印は障害なく
焼鈍分離剤が塗布できたことを示し、×印は乾燥後の密
着性が悪くコイルの巻き取りや搬送の際に焼鈍分離剤が
剥離してしまった場合を示す。同図より乾燥後の付着性
が悪い１〜５０μｍの粗粒アルミナであっても、１μｍ
未満の微粉アルミナを（Ｒ−１）％以上添加すれば付着
性が向上し、焼鈍分離剤として使用できることがわか
る。ここで、Ｒは粗粒アルミナの平均粒径（μｍ）であ
る。FIG. 1 shows the results of evaluating the operability in the coating process of the annealing separator of the grain-oriented silicon steel sheet by mixing various alumina powders having an average particle size of 1 to 50 μm with fine alumina particles of less than 1 μm to prepare a slurry. is there. The ∘ mark indicates that the annealing separating agent could be applied without any trouble, and the X mark indicates that the adhesiveness after drying was poor and the annealing separating agent was peeled off during coil winding or conveyance. As shown in the figure, even if the coarse-grained alumina of 1 to 50 μm has poor adhesion after drying, 1 μm
It can be seen that the addition of (R-1)% or more of finely divided alumina less than this improves the adhesion and can be used as an annealing separator. Here, R is the average particle diameter (μm) of coarse-grained alumina.
【００１８】粗粒アルミナに対する微粉アルミナの混合
比を増大させた場合、焼鈍分離剤のコストが増大するば
かりでなく、アルミナの鋼板への焼き付きが懸念され
る。そこで、各種粒径のアルミナに微粉アルミナを各種
の混合比で混合し、仕上げ焼鈍後の鋼板の酸素分析を行
った（表２）。表２より、１〜５０μｍの粗粒アルミナ
の混合比が５０％を超えると、仕上げ焼鈍後に鋼板にア
ルミナの焼き付きが起こることがわかる。When the mixing ratio of fine alumina to coarse-grained alumina is increased, not only the cost of the annealing separating agent increases but also seizure of alumina on the steel sheet is feared. Therefore, fine powder alumina was mixed at various mixing ratios with alumina having various particle sizes, and oxygen analysis was performed on the steel sheet after finish annealing (Table 2). From Table 2, it can be seen that when the mixing ratio of coarse-grained alumina having a particle size of 1 to 50 μm exceeds 50%, seizure of alumina occurs on the steel sheet after finish annealing.
【００１９】[0019]
【表２】 [Table 2]
【００２０】以上の検討により、平均粒径１〜５０μｍ
の粗粒アルミナ粉に、平均粒径１μｍ未満の微粉アルミ
ナを（Ｒ−１）％以上でかつ５０％以下混合した焼鈍分
離剤を用いるならば、鋼板に対する付着性が良好でかつ
仕上げ焼鈍時に焼き付きの極めて少ない方向性珪素鋼板
が製造できることがわかった。ただしＲは粗粒アルミナ
の平均粒径である。From the above examination, the average particle size is 1 to 50 μm.
If an annealing separator is used in which the fine alumina particles having an average particle size of less than 1 μm are mixed in an amount of (R-1)% or more and 50% or less with the coarse-grained alumina powder of No. 1, the adhesiveness to the steel sheet is good and the seizure occurs during finish annealing. It has been found that a grain-oriented silicon steel sheet having a very small amount can be manufactured. However, R is an average particle diameter of coarse-grained alumina.
【００２１】ところで、従来のＭｇＯを主体とする焼鈍
分離剤に代わってアルミナ系の焼鈍分離剤を用いた場
合、仕上げ焼鈍中での脱Ｓが十分に進行するか否かが懸
念される。発明者らの経験によれば、アルミナの焼き付
きが生ぜずかつ鋼板が金属光沢を呈している場合には、
仕上げ焼鈍中における脱Ｓは比較的スムーズに完了する
との傾向を認めている。しかしながら、確実な脱Ｓを行
うために、少量の脱Ｓ促進剤（ＭｇＯ，ＣａＯ，ＣａＳ
ｉＯ4 等）を焼鈍分離剤に添加することは本発明におけ
る効果を減ずるものではない。[0021] By the way, if an alumina-based annealing separator is used instead of the conventional MgO-based annealing separator, there is concern about whether S removal during the final annealing will proceed sufficiently. According to the experience of the inventors, when seizure of alumina does not occur and the steel sheet has a metallic luster,
It is recognized that the S removal during the finish annealing tends to be completed relatively smoothly. However, in order to perform reliable S removal, a small amount of S removal promoter (MgO, CaO, CaS
The addition of iO 4 etc.) to the annealing separator does not diminish the effect of the present invention.
【００２２】本発明は、仕上げ焼鈍により鋼板表面を鏡
面化し、極めて鉄損の低い方向性珪素鋼板を製造しよう
とする場合にも有効である。その場合には、実施例にお
いて示すように、脱炭焼鈍における酸素ポテンシャルを
脱炭に必要な最小限に抑えて酸化層形成を抑制させる
か、あるいは脱炭焼鈍後の鋼板に酸洗等を施して脱炭酸
化層を除去した後、本発明による焼鈍分離剤を塗布乾燥
して仕上げ焼鈍を行うと良い。また、焼鈍分離剤スラリ
ーに微量のインヒビターを添加するならば、なお一層仕
上げ焼鈍後の鏡面化が良好となる。The present invention is also effective when the surface of a steel sheet is mirror-finished by finish annealing to produce a grain-oriented silicon steel sheet having extremely low iron loss. In that case, as shown in the examples, the oxygen potential in decarburization annealing is suppressed to the minimum necessary for decarburization to suppress the formation of an oxide layer, or the steel sheet after decarburization annealing is subjected to pickling or the like. After removing the decarboxylated layer, the annealing separator according to the present invention may be applied and dried for finish annealing. Further, if a small amount of inhibitor is added to the annealing separator slurry, the mirror finish after the finish annealing becomes even better.
【００２３】[0023]
実施例１ Ｃ：０．０４６％、Ｓｉ：３．１２％、Ｍｎ：０．０５
７％、Ｓ：０．０２２％を含有し、残部がＦｅおよび不
可避的不純物よりなる珪素鋼熱延鋼帯を、９８０℃、３
分間の中間焼鈍を挟む２回の冷間圧延により板厚０．３
５mmの冷延板とし、ついで湿潤雰囲気中で脱炭焼鈍を行
った。ついでこの鋼板に表３に示す各種焼鈍分離剤を水
でスラリー化し、塗布乾燥の後、最終仕上げ焼鈍を行っ
た。Example 1 C: 0.046%, Si: 3.12%, Mn: 0.05
7%, S: 0.022%, the balance is made of Fe and inevitable impurities.
Plate thickness is 0.3 by two times cold rolling with intermediate annealing for 2 minutes.
A 5 mm cold-rolled sheet was prepared, and then decarburized and annealed in a wet atmosphere. Then, various annealing separators shown in Table 3 were slurried with water on this steel sheet, and after coating and drying, final finishing annealing was performed.
【００２４】その後、燐酸塩とコロイド状シリカを主成
分とするコーティング液を塗布焼き付けた。得られた各
種鋼板の外観、打ち抜き性、磁気特性を調べた結果も表
３に示す。表３における打ち抜き性は直径５mmのスチー
ルダイスにより打ち抜き作業を行った際に、返り高さが
５０μｍに達する打ち抜き回数でもって評価している。
表３から明らかなように、本発明による焼鈍分離剤を用
いるならば、打ち抜き性の格段に優れた方向性珪素鋼板
が得られる。Then, a coating liquid containing phosphate and colloidal silica as main components was applied and baked. Table 3 also shows the results of examining the appearance, punchability, and magnetic properties of the various steel sheets obtained. The punching property in Table 3 is evaluated by the number of punching times when the return height reaches 50 μm when punching work is performed with a steel die having a diameter of 5 mm.
As is clear from Table 3, if the annealing separator according to the present invention is used, a grain-oriented silicon steel sheet having markedly excellent punchability can be obtained.
【００２５】[0025]
【表３】 [Table 3]
【００２６】実施例２ Ｃ：０．０８％、Ｓｉ：３．３％、酸可溶性Ａｌ：０．
０２５％、Ｎ：０．００９％、Ｍｎ：０．０７％、Ｓ：
０．０１５％、Ｓｅ：０．０１５％、残部がＦｅおよび
不可避的不純物からなる珪素鋼熱延鋼帯を１１２０℃で
２分間焼鈍した後、冷間圧延して板厚０．２３mmとし、
ついで湿潤雰囲気中で脱炭焼鈍を行った。その後、フッ
酸中に浸漬することにより脱炭酸化膜を除去し、表４に
示す各種焼鈍分離剤を水で懸濁したスラリーを塗布、乾
燥の後、最終仕上げ焼鈍を行った。Example 2 C: 0.08%, Si: 3.3%, acid-soluble Al: 0.
025%, N: 0.009%, Mn: 0.07%, S:
0.015%, Se: 0.015%, the balance of the hot-rolled silicon steel strip made of Fe and unavoidable impurities is annealed at 1120 ° C. for 2 minutes, and then cold-rolled to a plate thickness of 0.23 mm,
Then, decarburization annealing was performed in a humid atmosphere. After that, the decarboxylated film was removed by immersing in hydrofluoric acid, and a slurry in which various annealing separators shown in Table 4 were suspended in water was applied and dried, followed by final finish annealing.
【００２７】さらに、燐酸塩とコロイド状シリカを主体
とするコーティング液を塗布焼き付け、レーザービーム
を照射して磁区細分化処理を行った。得られた鋼板の外
観、磁気特性等を表４に示す。表４から明らかなよう
に、脱炭焼鈍皮膜を除去した鋼板に本発明による焼鈍分
離剤を用いるならば、極めて鉄損の低い方向性電磁鋼板
が製造できる。Further, a coating solution containing phosphate and colloidal silica as a main component was applied and baked, and a laser beam was irradiated to perform magnetic domain subdivision processing. Table 4 shows the appearance and magnetic properties of the obtained steel sheet. As is clear from Table 4, if the annealing separator according to the present invention is used for the steel sheet from which the decarburization annealing film has been removed, a grain-oriented electrical steel sheet with extremely low iron loss can be produced.
【００２８】[0028]
【表４】 [Table 4]
【００２９】実施例３ Ｃ：０．０５％、Ｓｉ：３．３％、酸可溶性Ａｌ：０．
０２９％、Ｎ：０．００８％、Ｍｎ：０．１２％、Ｓ：
０．００７％、残部がＦｅおよび不可避的不純物よりな
る珪素鋼熱延鋼帯を１１００℃で２分間焼鈍した後、冷
間圧延して板厚０．１５mmとし、ついで湿潤雰囲気中で
脱炭焼鈍を行った。続いて二次再結晶を安定化させるた
めにアンモニア雰囲気中で窒化処理を行い、全窒素量を
１９０ppm とした。その後、フッ酸中に浸漬することに
より脱炭酸化膜を除去し、表５に示す各種焼鈍分離剤を
水で懸濁したスラリーを塗布、乾燥の後、最終仕上げ焼
鈍を行った。Example 3 C: 0.05%, Si: 3.3%, acid-soluble Al: 0.
029%, N: 0.008%, Mn: 0.12%, S:
A hot-rolled silicon steel strip containing 0.007% of balance Fe and unavoidable impurities is annealed at 1100 ° C. for 2 minutes, cold-rolled to a sheet thickness of 0.15 mm, and then decarburized and annealed in a wet atmosphere. I went. Subsequently, nitriding treatment was performed in an ammonia atmosphere to stabilize the secondary recrystallization, and the total nitrogen amount was set to 190 ppm. Then, the decarboxylated film was removed by immersing in hydrofluoric acid, and a slurry in which various annealing separators shown in Table 5 were suspended was applied, dried, and then subjected to final finish annealing.
【００３０】さらに、燐酸塩とコロイド状シリカを主体
とするコーティング液を塗布焼き付け、レーザービーム
を照射して磁区細分化処理を行った。得られた鋼板の外
観、磁気特性等を表５に示す。表４および表５から明ら
かなように、脱炭焼鈍皮膜を除去した鋼板に本発明によ
る焼鈍分離剤を用いるならば、極めて鉄損の低い方向性
電磁鋼板が製造できる。Further, a coating solution containing phosphate and colloidal silica as a main component was applied and baked, and a laser beam was irradiated to perform magnetic domain subdivision processing. Table 5 shows the appearance and magnetic properties of the obtained steel sheet. As is clear from Tables 4 and 5, if the annealing separator according to the present invention is used for the steel sheet from which the decarburization annealing film has been removed, a grain-oriented electrical steel sheet with extremely low iron loss can be produced.
【００３１】[0031]
【表５】 [Table 5]
【００３２】[0032]
【発明の効果】本発明による焼鈍分離剤を用いることに
より、グラス皮膜を生成させないことによる打ち抜き性
の良好な方向性珪素鋼板、あるいは鏡面を有する極めて
鉄損の低い方向性珪素鋼板を安価に製造することができ
る。EFFECTS OF THE INVENTION By using the annealing separator according to the present invention, it is possible to inexpensively produce a grain-oriented silicon steel sheet having a good punching property without forming a glass film or a grain-oriented grain-oriented silicon steel sheet having an extremely low iron loss. can do.
【図１】粗粒アルミナに微粉アルミナを混合させた焼鈍
分離剤を用いた場合の、操業性（アルミナの鋼板に対す
る付着性）を示す図表。FIG. 1 is a chart showing operability (adhesiveness of alumina to a steel sheet) when an annealing separating agent in which coarse alumina is mixed with fine alumina is used.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石橋 希瑞 北九州市戸畑区飛幡町１番１号 新日本製 鐵株式会社八幡製鐵所内 (72)発明者 美嶋 洋一 北九州市戸畑区飛幡町１番１号 新日本製 鐵株式会社八幡製鐵所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nozomi Ishibashi 1-1, Tobata-cho, Tobata-ku, Kitakyushu City In-house of Nippon Steel Yawata Works (72) Inventor Yoichi Mishima 1 Tobata-cho, Tobata-ku, Kitakyushu City No. 1 Nippon Steel Yawata Works Co., Ltd.
Claims (1)
に、平均粒径１μｍ未満の微粉アルミナを（Ｒ−１）％
でかつ５０％以下混合した、鋼板に対する付着性が良好
でかつ仕上げ焼鈍時に焼き付きの極めて少ない方向性珪
素鋼板用の焼鈍分離剤。ただしＲは粗粒アルミナの平均
粒径である。1. A coarse alumina powder having an average particle diameter of 1 to 50 μm and (R-1)% fine alumina powder having an average particle diameter of less than 1 μm.
And an admixture of 50% or less, which has good adhesion to a steel sheet and has extremely little seizure during finish annealing, and is an annealing separator for a oriented silicon steel sheet. However, R is an average particle diameter of coarse-grained alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16365993A JPH0718457A (en) | 1993-07-01 | 1993-07-01 | Separation agent at annealing for grain oriented silicon steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16365993A JPH0718457A (en) | 1993-07-01 | 1993-07-01 | Separation agent at annealing for grain oriented silicon steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0718457A true JPH0718457A (en) | 1995-01-20 |
Family
ID=15778147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16365993A Pending JPH0718457A (en) | 1993-07-01 | 1993-07-01 | Separation agent at annealing for grain oriented silicon steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0718457A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100435456B1 (en) * | 1999-11-30 | 2004-06-10 | 주식회사 포스코 | A method for manufacturing low temperature reheated grain-oriented electrical steel sheet having no glass film |
| WO2010015156A1 (en) * | 2008-08-08 | 2010-02-11 | 宝山钢铁股份有限公司 | A method of manufacturing oriented si steel containing cu |
| WO2020149328A1 (en) | 2019-01-16 | 2020-07-23 | 日本製鉄株式会社 | Grain-oriented electrical steel plate and method for producing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04259329A (en) * | 1991-02-12 | 1992-09-14 | Sumitomo Metal Ind Ltd | Production of grain-oriented silicon steel sheet excellent in blankability |
-
1993
- 1993-07-01 JP JP16365993A patent/JPH0718457A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04259329A (en) * | 1991-02-12 | 1992-09-14 | Sumitomo Metal Ind Ltd | Production of grain-oriented silicon steel sheet excellent in blankability |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100435456B1 (en) * | 1999-11-30 | 2004-06-10 | 주식회사 포스코 | A method for manufacturing low temperature reheated grain-oriented electrical steel sheet having no glass film |
| WO2010015156A1 (en) * | 2008-08-08 | 2010-02-11 | 宝山钢铁股份有限公司 | A method of manufacturing oriented si steel containing cu |
| US8231739B2 (en) | 2008-08-08 | 2012-07-31 | Baoshan Iron & Steel Co., Ltd. | Method for producing grain-oriented silicon steel containing copper |
| WO2020149328A1 (en) | 2019-01-16 | 2020-07-23 | 日本製鉄株式会社 | Grain-oriented electrical steel plate and method for producing same |
| KR20210110682A (en) | 2019-01-16 | 2021-09-08 | 닛폰세이테츠 가부시키가이샤 | A unidirectional electrical steel sheet and its manufacturing method |
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