JPH06100927A - Production of grain-oriented silicon steel sheet - Google Patents
Production of grain-oriented silicon steel sheetInfo
- Publication number
- JPH06100927A JPH06100927A JP5032299A JP3229993A JPH06100927A JP H06100927 A JPH06100927 A JP H06100927A JP 5032299 A JP5032299 A JP 5032299A JP 3229993 A JP3229993 A JP 3229993A JP H06100927 A JPH06100927 A JP H06100927A
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- Japan
- Prior art keywords
- annealing
- steel sheet
- primary recrystallization
- sio
- grain
- Prior art date
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- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、磁束密度が高く鉄損が
極めて低い方向性珪素鋼板（以下、方向性電磁鋼板と云
う）の製造方法に関するものである。特に、二次再結晶
工程（仕上げ焼鈍工程）で、その鋼板表面にフォルステ
ライト（以下、グラスと云う）被膜を形成させないかあ
るいは、サーマルエッチングにより鋼板表面を鏡面とし
た状態で同工程を完了させ、その後、磁区細分化、張力
コーティング等の処理を行い、鉄損特性の改善を図ろう
とするものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a grain-oriented silicon steel sheet (hereinafter referred to as grain-oriented electrical steel sheet) having a high magnetic flux density and an extremely low iron loss. In particular, in the secondary recrystallization process (finish annealing process), do not form a forsterite (hereinafter referred to as glass) coating on the steel plate surface, or complete the process with the steel plate surface mirror-finished by thermal etching. After that, the magnetic domain subdivision, the tension coating and the like are performed to improve the iron loss characteristics.
【０００２】[0002]
【従来の技術】方向性電磁鋼板は、電気機器の磁気鉄芯
として多用され、エネルギーロスを少なくすべく、改善
が繰り返されてきた。方向性電磁鋼板の鉄損を低減する
手段として、仕上げ焼鈍後の材料表面にレーザービーム
を照射し、局部歪を与え、それによって磁区を細分化し
て鉄損を低下させる方法が、例えば特開昭５８−２６４
０５号公報に開示されている。2. Description of the Related Art Grain-oriented electrical steel sheets are frequently used as magnetic iron cores for electric equipment and have been repeatedly improved in order to reduce energy loss. As a means for reducing the iron loss of grain-oriented electrical steel sheets, a method of irradiating a laser beam on the surface of the material after finish annealing to give local strain to thereby subdivide the magnetic domains to reduce the iron loss is disclosed in, for example, Japanese Patent Application Laid-Open No. 58-264
No. 05 publication.
【０００３】また局部歪は、通常行われる加工後の応力
除去焼鈍（歪取り焼鈍）によって除去されるので、磁区
細分化効果が消失する。この改善策、すなわち応力除去
焼鈍しても磁区細分化効果が消失しない手段が、例え
ば、特開昭６２−８６１７号公報に開示されている。Further, since the local strain is removed by the stress relief annealing (strain relief annealing) after the usual working, the magnetic domain refining effect disappears. This remedy, that is, means for preventing the magnetic domain refining effect from disappearing even when stress-relief annealing is disclosed, for example, in Japanese Patent Laid-Open No. 62-8617.
【０００４】さらに鉄損値の低減を図るためには、鋼板
表面近傍の磁区の動きを阻害する地鉄表面の凹凸を取り
除くこと（平滑化）が重要である。平滑化の最も高いレ
ベルが鏡面である。仕上げ焼鈍後の材料表面を平滑化
（鏡面化）する方法としては、特開昭６４−８３６２０
号公報に開示されている化学研磨、電解研磨等がある。In order to further reduce the iron loss value, it is important to remove (smooth) the irregularities on the surface of the base metal which hinder the movement of magnetic domains near the surface of the steel sheet. The highest level of smoothing is specular. As a method for smoothing (mirror-finishing) the material surface after finish annealing, there is disclosed in JP-A-64-83620.
There are chemical polishing, electrolytic polishing, and the like disclosed in the publication.
【０００５】[0005]
【発明が解決しようとする課題】従来、鋼板表面を鏡面
化（平滑化）する方法としては、前記化学研磨、電解研
磨の他にブラシ研磨、サンドペーパー研磨、研削等の化
学的あるいは物理的方法がある。しかしながら、これら
の方法は、小試片、少量の試料を作るには適するが、工
業的に多量生産される金属ストリップ等の表面鏡面化
（平滑化）のためには、諸々の困難を伴う。Conventionally, as a method of mirror-finishing (smoothing) the surface of a steel sheet, chemical or physical methods such as brush polishing, sandpaper polishing and grinding other than the above chemical polishing and electrolytic polishing are used. There is. However, these methods are suitable for producing small test pieces and small samples, but are accompanied by various difficulties for the surface mirror-finishing (smoothing) of industrially mass-produced metal strips and the like.
【０００６】最も平滑化できるとされる化学的方法、す
なわち、化学研磨においては、薬剤濃度管理、排水処理
等の環境問題、また物理的方法においては、工業的に大
きな面積を持つ表面を同一基準で平滑化（鏡面化）する
ことは、極めて困難である。本発明は、これらの問題を
排して、工業的生産規模で方向性電磁鋼板の表面を鏡面
化あるいは平滑化する方法を提供することを目的とす
る。当然ながら鏡面化あるいは平滑化のために、磁気特
性が失われてはならない。本発明においては、仕上げ焼
鈍工程で同時に目的を達成しようとするものである。す
なわち、二次再結晶の方位を制御し、極度に高い磁束密
度を得、かつ鏡面あるいは平滑表面を得ようとするもの
である。In the chemical method that is said to be the most smooth, that is, in chemical polishing, environmental problems such as chemical concentration control and wastewater treatment, and in the physical method, a surface having an industrially large area is used as the same standard. It is extremely difficult to smooth (mirror-finish) with. An object of the present invention is to eliminate these problems and to provide a method for mirror-finishing or smoothing the surface of a grain-oriented electrical steel sheet on an industrial production scale. Of course, the magnetic properties must not be lost due to mirroring or smoothing. In the present invention, the finish annealing process is intended to simultaneously achieve the purpose. That is, the orientation of secondary recrystallization is controlled to obtain an extremely high magnetic flux density and to obtain a mirror surface or a smooth surface.
【０００７】[0007]
【課題を解決するための手段】本発明の特徴とするとこ
ろは、前記するように仕上げ焼鈍時に鏡面あるいは平滑
表面を得るところにある。すなわち通常行われているＭ
ｇＯを主体とする焼鈍分離剤を用いずに、アルミナ（Ａ
ｌ2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ
2 ）、酸化ストロンチウム（ＳｒＯ）、及びフォルステ
ライト（Ｍｇ2ＳｉＯ4 ）等のＳｉＯ2 と反応しにくい
物質を主体とする焼鈍分離剤を用いて、仕上げ焼鈍し、
高い磁束密度の方向性電磁鋼板を得ると同時に鋼板の表
面にグラス（フォルステライト）被膜を形成させずに、
金属表面を露出させた状態で二次再結晶させ、同時に、
サーマルエッチングにより金属表面を鏡面あるいは平滑
化することを特徴とする。A feature of the present invention is to obtain a mirror surface or a smooth surface during finish annealing as described above. That is, M which is usually performed
Without using an annealing separator mainly composed of gO, alumina (A
l 2 O 3 ), silica (SiO 2 ), zirconia (ZrO
2), strontium oxide (SrO), and using an annealing separator composed forsterite (Mg 2 SiO 4) mainly nobler material and SiO 2 such as, finishing annealing,
At the same time as obtaining a grain-oriented electrical steel sheet with a high magnetic flux density, without forming a glass (forsterite) coating on the surface of the steel sheet,
Secondary recrystallization with the metal surface exposed, at the same time,
It is characterized in that the metal surface is mirror-finished or smoothed by thermal etching.
【０００８】ここでサーマルエッチングとは、鋼板の地
鉄を露出させ、鋼板（地鉄）表面に地鉄と反応するもの
が存在しない状態にしておいて、中性あるいは還元性雰
囲気中、二次再結晶が発現する温度以上の温度に鋼板を
加熱し、鋼板表面を平滑化（表面化）する処理をいう。The term "thermal etching" as used herein means that the base metal of the steel sheet is exposed, and the surface of the steel sheet (base iron) is free from any substance that reacts with the base iron. It is a treatment for heating the steel sheet to a temperature equal to or higher than the temperature at which recrystallization occurs so as to smooth (surface) the steel sheet surface.
【０００９】本発明は、珪素熱延鋼帯を必要に応じて焼
鈍した後、１回または中間焼鈍をはさむ２回以上の冷間
圧延を行い、所定の板厚とし、次いで一次再結晶焼鈍を
行った後焼鈍分離剤を塗布し、仕上げ焼鈍を施す方向性
珪素鋼板の製造プロセスにおいて、一次再結晶焼鈍後、
平均粒径が０．５〜１０．０μｍのアルミナ（Ａｌ2Ｏ
3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、
酸化ストロンチウム（ＳｒＯ）、及びフォルステライト
（Ｍｇ2 ＳｉＯ4 ）の１種あるいは２種以上を主成分と
する焼鈍分離剤を塗布し、中性あるいは、還元性雰囲気
で仕上げ焼鈍することである。According to the present invention, the hot-rolled silicon steel strip is annealed as required, and then cold-rolled once or twice or more with an intermediate anneal to obtain a predetermined plate thickness, and then a primary recrystallization anneal. In the manufacturing process of the grain-oriented silicon steel sheet after applying the annealing separator after performing the finish annealing, after the primary recrystallization annealing,
Alumina (Al 2 O having an average particle size of 0.5 to 10.0 μm)
3 ), silica (SiO 2 ), zirconia (ZrO 2 ),
This is to apply an annealing separator containing, as a main component, one or more of strontium oxide (SrO) and forsterite (Mg 2 SiO 4 ) and finish annealing in a neutral or reducing atmosphere.
【００１０】ここで、一次再結晶焼鈍後、該焼鈍工程で
生ずる鋼板表面の酸化膜を除去し、次いで平均粒径が
０．５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ3 ）、シリ
カ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ストロ
ンチウム（ＳｒＯ）、及びフォルステライト（Ｍｇ2 Ｓ
ｉＯ4 ）の１種あるいは２種以上を主成分とする焼鈍分
離剤を塗布し、中性あるいは、還元性雰囲気で仕上げ焼
鈍すること、一次再結晶焼鈍後、アンモニアガスによる
窒化処理を行い、インヒビターを強化して、しかる後、
平均粒径が０．５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ
3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、
酸化ストロンチウム（ＳｒＯ）、及びフォルステライト
（Ｍｇ2 ＳｉＯ4 ）の１種あるいは２種以上を主成分と
する焼鈍分離剤を塗布し、中性あるいは還元性雰囲気で
仕上げ焼鈍するものである。Here, after the primary recrystallization annealing, the oxide film on the surface of the steel sheet produced in the annealing step is removed, and then alumina (Al 2 O 3 ) and silica (SiO 2 ) having an average particle size of 0.5 to 10.0 μm are removed. 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 S)
(iO 4 ), an annealing separating agent containing one or more of them as a main component is applied, and finish annealing is performed in a neutral or reducing atmosphere. After primary recrystallization annealing, nitriding treatment with ammonia gas is performed to obtain an inhibitor. After strengthening,
Alumina (Al 2 O having an average particle size of 0.5 to 10.0 μm)
3 ), silica (SiO 2 ), zirconia (ZrO 2 ),
An annealing separator containing one or more of strontium oxide (SrO) and forsterite (Mg 2 SiO 4 ) as a main component is applied, and finish annealing is performed in a neutral or reducing atmosphere.
【００１１】さらに、本発明は、一次再結晶焼鈍後、ア
ンモニアガスによる窒化処理を行い、しかる後、一次再
結晶焼鈍工程で生じる鋼板表面の酸化膜を除去し、平均
粒径が０．５〜１０．０μｍのアルミナ（Ａｌ
2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（Ｚｒ
Ｏ2 ）、酸化ストロンチウム（ＳｒＯ）、及びフォルス
テライト（Ｍｇ2 ＳｉＯ4 ）の１種あるいは２種以上を
主成分とする焼鈍分離剤を塗布し、中性あるいは還元性
雰囲気で仕上げ焼鈍するものである。Further, in the present invention, after the primary recrystallization annealing, nitriding treatment with ammonia gas is performed, and thereafter, the oxide film on the surface of the steel sheet generated in the primary recrystallization annealing step is removed, and the average grain size is 0.5 to 0.5. 10.0 μm alumina (Al
2 O 3 ), silica (SiO 2 ), zirconia (Zr
O 2 ), strontium oxide (SrO), and forsterite (Mg 2 SiO 4 ), which are applied as a main component, or as an annealing separator, and finish-annealed in a neutral or reducing atmosphere. is there.
【００１２】さらに、本発明は、珪素熱延鋼帯の成分を
Ｓｉ：２．０〜４．８重量％、酸可溶性Ａｌ：０．００
８〜０．０５重量％、Ｎ≦０．０１０重量％、残部Ｆｅ
及び不可避的不純物とすることは極めて有効である。ま
た鋼板表面の酸化膜を除去する方法を酸洗とし、特にフ
ッ酸を混入した酸で酸洗することも有効である。Further, in the present invention, the components of the silicon hot rolled steel strip are Si: 2.0 to 4.8% by weight, acid-soluble Al: 0.00
8 to 0.05% by weight, N ≦ 0.010% by weight, balance Fe
In addition, it is extremely effective to use unavoidable impurities. It is also effective to use pickling as the method for removing the oxide film on the surface of the steel sheet, and particularly pickling with an acid mixed with hydrofluoric acid.
【００１３】焼鈍分離剤の塗布は、アルミナ（Ａｌ2 Ｏ
3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、
酸化ストロンチウム（ＳｒＯ）、及びフォルステライト
（Ｍｇ2 ＳｉＯ4 ）の平均粒径を０．５〜１０．０μｍ
とすることで、通常のＭｇＯを主体とする水スラリーと
同様に、水スラリー塗布とすることができる。The application of the annealing separator is performed by using alumina (Al 2 O
3 ), silica (SiO 2 ), zirconia (ZrO 2 ),
The average particle size of strontium oxide (SrO) and forsterite (Mg 2 SiO 4 ) is 0.5 to 10.0 μm.
Thus, the water slurry can be applied in the same manner as the normal water-based slurry mainly containing MgO.
【００１４】なお、一次再結晶焼鈍後のアンモニアガス
によるインヒビター強化及び仕上げ焼鈍雰囲気の窒素分
圧操作は、冷延鋼板に酸可溶性Ａｌを含むとき極めて有
効であるが、酸可溶性Ａｌを含まないときは、その効果
は小さい。しかし、不可避的に存在する窒化物形成元素
に窒素が作用し析出物量を増し、インヒビターを強化す
る。[0014] It should be noted that the inhibitor strengthening with ammonia gas after the primary recrystallization annealing and the nitrogen partial pressure operation in the finish annealing atmosphere are extremely effective when the cold-rolled steel sheet contains acid-soluble Al, but do not contain acid-soluble Al. , Its effect is small. However, nitrogen acts on the inevitably present nitride-forming elements to increase the amount of precipitates and strengthen the inhibitor.
【００１５】以下、本発明について詳細に説明する。本
発明者等は、仕上げ焼鈍中のインヒビター劣化の律速過
程を詳しく調査したところ、熱延鋼板成分にＡｌを含む
場合には鋼板界面におけるＡｌの酸化過程が最大の因子
であり、一次再結晶焼鈍時生ずる鋼板表面の酸化層がイ
ンヒビターの劣化に大きく関与していることを見出し
た。The present invention will be described in detail below. The present inventors have investigated in detail the rate-determining process of inhibitor deterioration during finish annealing, and when Al is contained in the components of the hot-rolled steel sheet, the oxidation process of Al at the steel sheet interface is the largest factor, and the primary recrystallization annealing is performed. It was found that the oxide layer on the surface of the steel sheet, which occurs occasionally, is greatly involved in the deterioration of the inhibitor.
【００１６】一方、熱延鋼板成分にＡｌを含まず、イン
ヒビターとして、ＭｎＳ，ＭｎＳｅ，ＭｎＳｂ等を含む
場合は、温度上昇による析出物の溶解、あるいは析出物
の粗大化いわゆるオストワルド成長によりインヒビター
強度の劣化することが分かった。従って、二次再結晶に
対する鋼板表面（界面）の影響はあまり大きくなく、一
次再結晶焼鈍時生ずる鋼板表面の酸化層を除去しても、
しなくても、大きな影響がない。On the other hand, in the case where the hot rolled steel sheet component does not contain Al but contains MnS, MnSe, MnSb, etc. as an inhibitor, the inhibitor strength is increased by dissolution of the precipitate due to temperature increase or coarsening of the precipitate, so-called Ostwald growth. It turned out to deteriorate. Therefore, the influence of the steel sheet surface (interface) on the secondary recrystallization is not so large, and even if the oxide layer on the steel sheet surface generated during the primary recrystallization annealing is removed,
If you don't, it won't have a big impact.
【００１７】まず、熱延鋼帯成分にＡｌを含む場合につ
いて述べる。本発明者等は、仕上げ焼鈍中のインヒビタ
ー劣化の律速過程を詳しく調査したところ、鋼板界面に
おけるＡｌの酸化過程が最大の因子であり、一次再結晶
焼鈍時生ずる鋼板表面の酸化層がインヒビターの劣化に
大きく関与していることを見出した。First, the case where the hot-rolled steel strip component contains Al will be described. The present inventors have conducted a detailed investigation on the rate-determining process of inhibitor deterioration during finish annealing. As a result, the largest factor is the oxidation process of Al at the steel sheet interface, and the oxide layer on the surface of the steel sheet that occurs during primary recrystallization annealing deteriorates the inhibitor. I was found to be heavily involved in.
【００１８】Ｓｉ：３．３重量％、酸可溶性Ａｌ：０．
０２８重量％、Ｎ：０．００８重量％、Ｍｎ：０．１４
重量％、Ｓ：０．００７重量％、Ｃ：０．０５重量％、
残部Ｆｅ及び不可避的不純物からなる珪素熱延鋼帯を１
１００℃で２分間焼鈍した後、冷間圧延し、０．２３mm
厚とした。これらの冷延板を、脱炭を兼ねるために湿水
雰囲気とした焼鈍炉で８００℃で２分間焼鈍し、一次再
結晶させた。Si: 3.3% by weight, acid-soluble Al: 0.
028% by weight, N: 0.008% by weight, Mn: 0.14
% By weight, S: 0.007% by weight, C: 0.05% by weight,
1 hot-rolled silicon steel strip consisting of the balance Fe and unavoidable impurities
0.23mm after cold-rolling after annealing at 100 ℃ for 2 minutes
Made thick These cold-rolled sheets were annealed at 800 ° C. for 2 minutes in an annealing furnace in a wet water atmosphere in order to also serve as decarburization, and primary recrystallization was performed.
【００１９】次に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１８０pp
m とし、インヒビターを強化した。その後、そのま
ま、及び０．５％フッ酸−５％硫酸混合溶液で酸洗し
た、２種の材料にＡｌ2 Ｏ3 を静電塗布し、１００％Ｈ
2 雰囲気で、１５℃／Hrの昇温速度を保ちながら仕上げ
焼鈍を行った。Next, in order to stabilize the secondary recrystallization, nitriding treatment is performed in an ammonia atmosphere, and the total nitrogen amount is 180 pp.
m and strengthened the inhibitor. After that, Al 2 O 3 is electrostatically applied to the two materials, which have been pickled as they are and with a 0.5% hydrofluoric acid-5% sulfuric acid mixed solution, and 100% H
Finish annealing was performed in two atmospheres while maintaining a temperature rising rate of 15 ° C / Hr.
【００２０】仕上げ焼鈍中のインヒビター（ＡｌＮ，
（Ａｌ，Ｓｉ）Ｎ等）を調べたところ、図１に示すよう
に、一次再結晶焼鈍時鋼板表面に生ずる酸化層を有する
の材料は、酸化層のないの材料に比べて、インヒビ
ター強度が早く劣化することが分かった。Inhibitors (AlN,
(Al, Si) N, etc.), as shown in FIG. 1, the material having an oxide layer formed on the surface of the steel sheet during primary recrystallization annealing has a higher inhibitor strength than the material having no oxide layer. It turns out that it deteriorates quickly.
【００２１】すなわち、一次再結晶焼鈍時鋼板表面に生
ずる酸化層を除去すれば、高温まで強いインヒビター強
度が保持できるのである。鋼板中の酸可溶性Ａｌは、仕
上げ焼鈍中でＳｉＯ2 を主体とする酸化層から酸素をと
りＡｌ2 Ｏ3 等となって酸化層中に析出する。従って鋼
板中の酸可溶性Ａｌは、減少していく。なお、図１で
は、インヒビター強度として鋼中酸可溶性Ａｌ濃度を示
したが、Ａｌは、ＡｌＮ，（Ａｌ，Ｓｉ）Ｎ等の化合物
（析出物）を形成して、インヒビターとなっているの
で、酸可溶性Ａｌ量がインヒビター強度を示す指標と考
えて良い。That is, if the oxide layer formed on the surface of the steel sheet during the primary recrystallization annealing is removed, strong inhibitor strength can be maintained up to a high temperature. The acid-soluble Al in the steel sheet takes oxygen from the oxide layer mainly composed of SiO 2 during finish annealing to become Al 2 O 3 etc. and precipitates in the oxide layer. Therefore, the acid-soluble Al in the steel sheet decreases. In addition, in FIG. 1, the acid-soluble Al concentration in the steel is shown as the inhibitor strength, but since Al forms a compound (precipitate) such as AlN, (Al, Si) N, and acts as an inhibitor, It can be considered that the amount of acid-soluble Al is an index showing the inhibitor strength.
【００２２】さらに、本発明者等は、インヒビター劣化
の律速過程を詳しく調査したところ、前記の鋼板界面に
おけるＡｌの酸化以外に鋼中窒素及び焼鈍雰囲気中の窒
素量にも影響されることが分かった。なお、焼鈍雰囲気
中の窒素量は鋼板界面を通して鋼中の窒素量を増加させ
ているものであり、その効果は当初から鋼中に入ってい
る窒素と同じである。鋼中窒素及び焼鈍雰囲気中の窒素
は、ＡｌＮ等の析出物を増加させてＡｌを固定し、Ａｌ
の鋼板界面への移動を少なくするために、Ａｌの酸化が
抑制されるのである。従って、仕上げ焼鈍中の鋼中酸可
溶性Ａｌ量は、窒素分圧の高い方が、劣化は少なく、高
温までインヒビターは強い。Further, the inventors of the present invention have conducted a detailed investigation of the rate-determining process of inhibitor degradation, and found that the amount of nitrogen in the steel and the amount of nitrogen in the annealing atmosphere are also affected in addition to the oxidation of Al at the steel sheet interface. It was The amount of nitrogen in the annealing atmosphere increases the amount of nitrogen in the steel through the steel sheet interface, and the effect is the same as nitrogen contained in the steel from the beginning. Nitrogen in steel and nitrogen in the annealing atmosphere increase precipitates such as AlN to fix Al,
Oxidation of Al is suppressed in order to reduce the movement of Al to the steel sheet interface. Therefore, as for the amount of acid-soluble Al in steel during finish annealing, the higher the nitrogen partial pressure is, the less the deterioration is, and the stronger the inhibitor is at high temperature.
【００２３】本発明の主旨とするところの１つである高
い磁束密度を得るためには、インヒビターは、強い方が
良いのであるが、強く一定に維持されることが望まし
い。これは、二次再結晶開始から終了まで方位の良い結
晶（ＧＯＳＳ粒）のみを成長させるためであり、二次再
結晶開始から終了までにインヒビターが弱体化すると方
位の悪い粒まで成長し、製品鋼板の磁束密度が下がる。In order to obtain a high magnetic flux density, which is one of the main points of the present invention, it is preferable that the inhibitor is strong, but it is desirable that the inhibitor be strongly and constantly maintained. This is because only crystals with good orientation (GOSS grains) grow from the start to the end of secondary recrystallization, and if the inhibitor weakens from the start to the end of secondary recrystallization, grains with bad orientation grow and The magnetic flux density of the steel plate decreases.
【００２４】インヒビターであるＡｌＮの溶解度は、当
然ながら鋼板温度の上昇と共に大きくなり、必然的にイ
ンヒビターは劣化する。この方策として、温度が上昇す
るに従い窒素の分圧を上げて鋼板中の窒素量を増やし、
析出物としてのＡｌＮを一定に維持することが望まし
い。しかしながら本発明の主旨とするところの１つであ
る鏡面を得るには、窒素分圧があまり高くなり過ぎては
いけない。インヒビターを一定の強さで二次再結晶させ
るという点でＡｌＮの溶解度が変化しない、すなわちイ
ンヒビター強度が変わらない一定温度での二次再結晶
は、極めて有効である。The solubility of the inhibitor AlN naturally increases as the temperature of the steel sheet rises, and the inhibitor inevitably deteriorates. As a measure for this, as the temperature rises, the partial pressure of nitrogen is increased to increase the amount of nitrogen in the steel sheet,
It is desirable to keep AlN as a precipitate constant. However, the nitrogen partial pressure must not be too high in order to obtain a mirror surface, which is one of the gist of the present invention. Secondary recrystallization at a constant temperature at which the solubility of AlN does not change, that is, the inhibitor strength does not change, is extremely effective in that the inhibitor is secondarily recrystallized at a constant strength.
【００２５】前記するようにＡｌＮの溶解度は、一定温
度に保持すれば変わらないが、酸可溶性Ａｌは雰囲気中
の酸素あるいは、鋼板表面のＡｌより酸素親和性の小さ
い元素の酸化物より酸素をとり、Ａｌ2 Ｏ3 となって減
少していき、インヒビターは劣化する。従って、この場
合も窒素分圧を上げてＡｌＮの溶解を抑え、酸可溶性Ａ
ｌの減少を抑制しなければならない。As described above, the solubility of AlN does not change if it is maintained at a constant temperature, but the acid-soluble Al takes up oxygen in the atmosphere or oxygen from an oxide of an element having a smaller oxygen affinity than Al on the surface of the steel sheet. , Al 2 O 3 and decrease, and the inhibitor deteriorates. Therefore, also in this case, the partial pressure of nitrogen is increased to suppress the dissolution of AlN, and the acid-soluble A
The decrease in l must be suppressed.
【００２６】次に、熱延鋼板成分にＡｌを含まない場合
について述べる。前記するように熱延鋼板成分にＡｌを
含まないような珪素鋼板では、インヒビターとしては
Ｓ，Ｓｅ，Ｔｅ，Ｓｂ等を添加して、ＭｎＳ，ＭｎＳ
ｅ，ＭｎＴｅ，ＭｎＳｂ等を析出させ、インヒビターと
して用いるのが普通である。Next, the case where the hot rolled steel sheet component does not contain Al will be described. As described above, in the case of a silicon steel sheet in which the hot-rolled steel sheet component does not contain Al, S, Se, Te, Sb, etc. are added as inhibitors to add MnS, MnS.
It is common to precipitate e, MnTe, MnSb, etc. and use them as inhibitors.
【００２７】これらの析出物はＡｌのように鋼板界面か
らの脱離によってインヒビターが劣化することはなく、
鋼板温度の上昇による溶解度の上昇で析出物の減少、あ
るいは析出物のオストワルド成長による析出物平均粒径
の粗大化で、インヒビター効果強度は劣化する。従っ
て、一次再結晶焼鈍後に、該焼鈍で生成する鋼板表面の
酸化膜の存在に関わらずインヒビターの挙動はほぼ一定
である。These precipitates do not deteriorate the inhibitor due to desorption from the steel sheet interface unlike Al,
The inhibitor effect strength deteriorates due to the decrease in precipitates due to the increase in solubility due to the increase in the steel plate temperature or the coarsening of the precipitate average particle size due to the Ostwald growth of the precipitates. Therefore, after the primary recrystallization annealing, the behavior of the inhibitor is almost constant regardless of the presence of the oxide film on the surface of the steel sheet formed by the annealing.
【００２８】Ｓｉ：３．２重量％、Ｎ：０．００８重量
％、Ｍｎ：０．０８重量％、Ｓ：０．０２７重量％、
Ｃ：０．０５重量％、残部Ｆｅ及び不可避的不純物から
なる珪素熱延鋼帯を０．２３mmまで冷間圧延し、前記同
様、脱炭を兼ねるために湿水雰囲気とした焼鈍炉で８０
０℃で２分間焼鈍し、一次再結晶させた。Si: 3.2% by weight, N: 0.008% by weight, Mn: 0.08% by weight, S: 0.027% by weight,
C: 0.05% by weight of silicon, the hot-rolled silicon steel strip consisting of the balance Fe and unavoidable impurities was cold-rolled to 0.23 mm, and in the same manner as described above, it was heated in an annealing furnace in a wet water atmosphere for decarburization to 80
It was annealed at 0 ° C. for 2 minutes for primary recrystallization.
【００２９】その後、そのまま、及び０．５％フッ
酸−５％硫酸混合溶液で酸洗した２種の材料にＡｌ2 Ｏ
3 を静電塗布し、１００％Ｈ2 雰囲気で、１５℃／Hrの
昇温速度を保ちながら仕上げ焼鈍を行った。仕上げ焼鈍
中のＳを分析し、図２を得た。酸洗の有り無しに関わら
ず、比較的高温までＳが減少しないことが分かる。しか
し、これはインヒビター強度が共に高温まで強いことを
意味しない。その理由は前記の通り、析出物の溶解、及
び析出物のオストワルド成長による粗大化である。Then, Al 2 O was added to the two materials, which were pickled as they were and with a 0.5% hydrofluoric acid-5% sulfuric acid mixed solution.
3 was electrostatically applied, and finish annealing was performed in a 100% H 2 atmosphere while maintaining a temperature rising rate of 15 ° C./Hr. The S during finish annealing was analyzed, and FIG. 2 was obtained. It can be seen that S does not decrease up to a relatively high temperature with or without pickling. However, this does not mean that both inhibitor strengths are strong up to high temperatures. The reason is, as described above, the dissolution of the precipitate and the coarsening of the precipitate due to Ostwald growth.
【００３０】本発明における鋼成分は、Ｓｉ：２．０〜
４．８重量％、インヒビター構成元素として、酸可溶性
Ａｌ，Ｍｎ，Ｓ，Ｓｅ，Ｓｂ，Ｐ，Ｂ，Ｓｎ，Ｂｉ，Ｎ
ｂ，Ｔｉ，Ｍｏ，Ｃｕ等の１種あるいは２種以上が添加
される。Ｓｉは、電気抵抗を高め鉄損を下げるうえで重
要であるが、４．８重量％超では、冷間圧延時に割れ易
くなる。一方、２．０重量％未満では、電気抵抗が低く
鉄損を下げるうえで問題がある。The steel composition in the present invention is Si: 2.0-
4.8% by weight, acid-soluble Al, Mn, S, Se, Sb, P, B, Sn, Bi, N as an inhibitor constituent element
One or more of b, Ti, Mo and Cu are added. Si is important for increasing the electric resistance and decreasing the iron loss, but if it exceeds 4.8% by weight, it tends to crack during cold rolling. On the other hand, if it is less than 2.0% by weight, there is a problem in that the electric resistance is low and the iron loss is lowered.
【００３１】次にインヒビター構成元素について述べ
る。酸可溶性Ａｌは、インヒビター構成元素として重要
であり、窒素、珪素等と化合して、ＡｌＮ，（Ａｌ，Ｓ
ｉ）Ｎ等の析出物を作りインヒビターの役割を果たす。
インヒビター強度の面、すなわち、磁束密度が高くなる
範囲として、０．００８〜０．０５重量％である。Next, the inhibitor constituent elements will be described. Acid-soluble Al is important as an inhibitor constituent element, and is combined with nitrogen, silicon, etc. to form AlN, (Al, S
i) It forms a precipitate such as N and plays a role of an inhibitor.
In terms of inhibitor strength, that is, the range in which the magnetic flux density is high, it is 0.008 to 0.05% by weight.
【００３２】窒素は０．０１０重量％超では、ブリスタ
ーと呼ばれる空孔を鋼板中に生ずるので、この範囲が最
適である。その他インヒビター成分としてはＭｎ：０．
０３〜０．４０重量％、Ｓ：０．０１〜０．０５重量
％、Ｓｅ：０．０１〜０．１０重量％、Ｓｂ：０．０１
〜０．１０重量％の範囲で１種あるいは２種以上が添加
される。さらにＳｎ，Ｂｉ，Ｎｂ，Ｔｉ，Ｐ，Ｍｏ，Ｃ
ｕ等がインヒビター構成あるいは、補助元素として用い
られる。なお、炭素は０．０８５重量％以下が望まし
い。When the content of nitrogen exceeds 0.010% by weight, holes called blister are generated in the steel sheet, so this range is optimal. Other inhibitor components include Mn: 0.
03-0.40% by weight, S: 0.01-0.05% by weight, Se: 0.01-0.10% by weight, Sb: 0.01
In the range of 0.10% by weight, one kind or two or more kinds are added. Furthermore, Sn, Bi, Nb, Ti, P, Mo, C
u or the like is used as an inhibitor constituent or an auxiliary element. The carbon content is preferably 0.085% by weight or less.
【００３３】発明者等は焼鈍分離剤としてのアルミナ
（Ａｌ2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（Ｚ
ｒＯ2 ）、酸化ストロンチウム（ＳｒＯ）、及びフォル
ステライト（Ｍｇ2 ＳｉＯ4 ）の塗布方法について検討
した。静電塗布は仕上げ焼鈍炉内に水分を持ち込まない
方法として優れているが、通常用いられているＭｇＯを
主体とする焼鈍分離剤の塗布方法に比べて、塗布装置の
煩雑さ、設備費、粉末飛散による作業環境の悪化等の不
都合がある。The inventors have found that alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (Z) as an annealing separator.
The coating methods of rO 2 ), strontium oxide (SrO), and forsterite (Mg 2 SiO 4 ) were examined. Electrostatic coating is excellent as a method that does not bring moisture into the finish annealing furnace, but compared to the commonly used coating method for annealing separating agent mainly composed of MgO, the complexity of coating equipment, equipment cost, powder There are inconveniences such as deterioration of the work environment due to scattering.
【００３４】発明者等は、ＭｇＯを主体とする焼鈍分離
剤の塗布方法と同じ方法、すなわち水スラリーで塗布す
ることを検討し、アルミナ（Ａｌ2 Ｏ3 ）、シリカ（Ｓ
ｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ストロンチウ
ム（ＳｒＯ）、及びフォルステライト（Ｍｇ2 Ｓｉ
Ｏ4 ）の平均粒径がある範囲で、それが可能であること
を見出した。すなわち、これらの物質の平均粒径が０．
５〜１０．０μｍの時に良好な結果が得られることが分
かった。The inventors examined the same method as the method of applying the annealing separator mainly composed of MgO, that is, the application with water slurry, and confirmed that alumina (Al 2 O 3 ) and silica (S
iO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 Si)
It has been found that this is possible within a certain range of the average particle size of O 4 ). That is, the average particle size of these substances is 0.
It was found that good results were obtained when the thickness was 5 to 10.0 μm.
【００３５】０．５μｍ未満の粉末では、水スラリーと
して有効に塗布できるが、アルミナ（Ａｌ2 Ｏ3 ）、シ
リカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化スト
ロンチウム（ＳｒＯ）、及びフォルステライト（Ｍｇ2
ＳｉＯ4 ）の粒子自体は平均粒径が小さくなっているた
め活性化しているので焼結して被膜を形成してしまい、
金属面を現さなくなる。A powder of less than 0.5 μm can be effectively applied as a water slurry, but alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite ( Mg 2
The particles themselves of SiO 4 ) are activated because they have a small average particle size, so they are sintered and form a film,
The metal surface disappears.
【００３６】また、１０．０μｍ超では、水スラリー
が不安定で、撹拌が止まると直ちに沈澱してしまい、塗
布しにくい、粒子が粗いため鋼板表面にくい込んで、
平滑面が得られないだけでなく、磁気特性が劣化すると
いう問題を生じた。この現象は水スラリーの場合だけで
なく、粉体塗布、例えば、前記する静電塗布の場合でも
同じことが起こる。On the other hand, if it exceeds 10.0 μm, the water slurry is unstable and precipitates immediately when stirring is stopped, which is difficult to apply, and since the particles are coarse, the surface of the steel sheet is difficult to be embedded.
Not only a smooth surface cannot be obtained, but also magnetic properties are deteriorated. This phenomenon occurs not only in the case of water slurry but also in the case of powder coating, for example, electrostatic coating described above.
【００３７】すなわち、アルミナ（Ａｌ2 Ｏ3 ）、シリ
カ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ストロ
ンチウム（ＳｒＯ）、及びフォルステライト（Ｍｇ2 Ｓ
ｉＯ4 ）の平均粒径が小さい時は塗布し易いが、前記同
様平均粒径０．５μｍ未満では、焼結して被膜を形成し
てしまい、金属面を現さなくなり、また、平均粒径１
０．０μｍ超では、塗布装置への粉体の供給が難し
く、塗布しにくいばかりでなく、粒子の質量と帯電量の
関係で付着しにくく、付着してもすぐに脱着してしま
う、粒子が粗いため鋼板表面にくい込んで、平滑面が
得られないだけでなく、磁気特性が劣化するという問題
を生じた。That is, alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 S).
When the average particle size of i0 4 ) is small, it is easy to apply, but when the average particle size is less than 0.5 μm, the film is sintered and a coating film is not formed, and the metal surface is not exposed.
If the particle size exceeds 0.0 μm, it is difficult to supply the powder to the coating device, and it is difficult to apply the powder. In addition, it is difficult to adhere due to the relationship between the mass of the particle and the charge amount. Since it is rough, the surface of the steel sheet is difficult to penetrate, and not only a smooth surface cannot be obtained, but also the magnetic characteristics deteriorate.
【００３８】水スラリー塗布以外の塗布方法の場合もア
ルミナ（Ａｌ2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニ
ア（ＺｒＯ2 ）、酸化ストロンチウム（ＳｒＯ）、及び
フォルステライト（Ｍｇ2 ＳｉＯ4 ）の平均粒径は０．
５〜１０．０μｍが良い。ここで平均粒径と称している
のは重量で５０％通過する粒径である。なお、アルミナ
（Ａｌ2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（Ｚ
ｒＯ2 ）、酸化ストロンチウム（ＳｒＯ）、及びフォル
ステライト（Ｍｇ2 ＳｉＯ4 ）の１種あるいは２種以上
を主成分とする焼鈍分離剤に若干の防錆剤等を添加して
も差し障りない。In the case of coating methods other than the water slurry coating, the average of alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 SiO 4 ). The particle size is 0.
5 to 10.0 μm is preferable. Here, what is referred to as an average particle diameter is a particle diameter at which 50% by weight passes. Alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (Z
There is no problem even if a small amount of rust preventive agent or the like is added to the annealing separator containing at least one of rO 2 ), strontium oxide (SrO), and forsterite (Mg 2 SiO 4 ).
【００３９】以下、実施条件について述べる。一次再結
晶焼鈍時、鋼板表面にできる酸化層は、仕上げ焼鈍時に
次の２つに影響する。すなわち、前記するようにイン
ヒビター強度を弱め、十分な磁束密度が得られない、
製品の表面の平滑度が不十分で、磁気特性に悪影響を与
え、極限の磁気特性が出にくい。従って、究極の磁気特
性を得るためには、一次再結晶焼鈍時、鋼板表面にでき
る酸化層を除去することが望ましい。The implementation conditions will be described below. The oxide layer formed on the surface of the steel sheet during the primary recrystallization annealing affects the following two during the finish annealing. That is, as described above, the inhibitor strength is weakened and a sufficient magnetic flux density cannot be obtained.
The smoothness of the surface of the product is insufficient, which adversely affects the magnetic properties and makes it difficult to obtain the ultimate magnetic properties. Therefore, in order to obtain the ultimate magnetic properties, it is desirable to remove the oxide layer formed on the surface of the steel sheet during the primary recrystallization annealing.
【００４０】除去する方法としては、機械研磨、例え
ば、ブラシ研磨、サンドペーパー研磨、研削等があり、
本目的には有効であるが、工業上種々の困難を伴いあま
り実用的でない。本発明者等は、酸洗による方法が極め
て有効であることに気付いた。これは、熱延鋼帯あるい
は、鋼板等の連続酸洗ラインが既に実用化されているか
らである。また、酸洗液（酸洗溶液）としては、塩酸、
硫酸、硝酸等の鉱酸が有効であるが、鋼板表面にできる
酸化層は、主にＳｉＯ2 を主体とした酸化物であるため
に塩酸、硫酸、硝酸等の鉱酸だけでは、酸洗しにくい。
これらの酸にフッ酸を混合すると極めて効率的、すなわ
ち、高速で酸化層を除去することができる。As a method of removing, there are mechanical polishing, for example, brush polishing, sandpaper polishing, grinding, etc.
Although it is effective for this purpose, it is not very practical due to various industrial difficulties. The present inventors have found that the method of pickling is extremely effective. This is because a continuous pickling line for hot-rolled steel strips or steel plates has already been put to practical use. As the pickling solution (pickling solution), hydrochloric acid,
Although mineral acids such as sulfuric acid and nitric acid are effective, the oxide layer formed on the surface of the steel sheet is an oxide mainly composed of SiO 2 and therefore pickling with only mineral acids such as hydrochloric acid, sulfuric acid and nitric acid. Hateful.
When hydrofluoric acid is mixed with these acids, the oxide layer can be removed very efficiently, that is, at high speed.
【００４１】また、窒化物をインヒビターとする場合
は、一次再結晶焼鈍後から仕上げ焼鈍前にアンモニアに
より窒化処理を行い、インヒビターを強化することは有
効である。これは一次再結晶完了時のインヒビター強度
では、二次再結晶のためには不十分で、また仕上げ焼鈍
中の窒素分圧を上げてインヒビターを強化あるいは、劣
化防止しても二次再結晶時に十二分なインヒビターを確
保できない。When a nitride is used as an inhibitor, it is effective to strengthen the inhibitor by performing a nitriding treatment with ammonia after the primary recrystallization annealing and before the finish annealing. This is because the inhibitor strength at the time of completion of primary recrystallization is not sufficient for secondary recrystallization, and the nitrogen partial pressure during finish annealing is increased to strengthen the inhibitor or prevent deterioration even during secondary recrystallization. We cannot secure enough inhibitors.
【００４２】このため一般にアンモニア処理によるイン
ヒビター強化が、磁気特性を向上させる。二次再結晶進
行時に必要なインヒビターを確保するために、昇温時に
焼鈍雰囲気中に窒素ガスを５％以上９５％以下入れるの
が望ましいが、水素ガス１００％でも良い。なお、窒素
ガス５％未満では、インヒビターの強化あるいは、劣化
防止には効果が薄い。窒化物をインヒビターとしない場
合は、窒素分圧の効果は薄い。Therefore, strengthening the inhibitor by treating with ammonia generally improves the magnetic properties. In order to secure an inhibitor necessary for the progress of secondary recrystallization, it is desirable to add 5% or more and 95% or less of nitrogen gas in the annealing atmosphere at the time of temperature increase, but 100% of hydrogen gas may be used. If the nitrogen gas content is less than 5%, the effect of strengthening the inhibitor or preventing deterioration is small. If nitride is not the inhibitor, the effect of nitrogen partial pressure is weak.
【００４３】なお、中性あるいは、還元性雰囲気とは、
窒素、酸素、水分、水素、アルゴン等の不活性ガスの内
から１種あるいは２種以上のガスの混合物で珪素の酸化
還元に対して中性あるいは還元性であるガス組成をい
う。一般に電磁鋼板の仕上げ焼鈍では窒素及び水素ガス
が用いられるので、この両ガスの０％から１００％まで
の組み合わせである。The neutral or reducing atmosphere means
A gas composition which is neutral or reducing with respect to redox of silicon, which is a mixture of one or more gases selected from inert gases such as nitrogen, oxygen, water, hydrogen, and argon. Generally, nitrogen and hydrogen gas are used in the finish annealing of the electromagnetic steel sheet, so that the combination of these gases is 0% to 100%.
【００４４】窒素分圧を調整するために、この両ガスの
組み合わせにアルゴン、ヘリウム等の不活性ガスを混合
しても何等支障はない。中性あるいは還元性雰囲気とす
るのは、鋼中Ａｌの減少防止及び、鋼中の珪素を酸化さ
せて表面にＳｉＯ2 を造らないあるいは、増加させない
ためである。なお、二次再結晶完了後、純化及び鋼板表
面の鏡面化を完全にするために水素濃度を上げ、１２０
０℃付近で数時間保持することは、極めて有効である。There is no problem even if an inert gas such as argon or helium is mixed with the combination of both gases in order to adjust the nitrogen partial pressure. The neutral or reducing atmosphere is used to prevent reduction of Al in steel and to oxidize silicon in steel so as not to produce or increase SiO 2 on the surface. After the completion of secondary recrystallization, the hydrogen concentration was increased to 120% in order to complete the purification and the mirror-finishing of the steel plate surface.
Holding at around 0 ° C for several hours is extremely effective.
【００４５】仕上げ焼鈍における二次再結晶可能な温度
までの昇温速度は、高速であればあるほどインヒビター
の劣化が少なく好都合であった。昇温速度１５℃／Hr未
満では、インヒビターの劣化が著しく二次再結晶時に必
要なインヒビターが十分確保されず、十分な二次再結晶
が得られなかった。本発明の主旨の１つである高い磁束
密度を得るという点では、５０℃／Hr以上の昇温速度が
望ましい。The higher the rate of temperature rise to the temperature at which secondary recrystallization is possible in the finish annealing, the more convenient the inhibitor is because it is less likely to deteriorate. When the temperature rising rate is less than 15 ° C./Hr, the inhibitor was remarkably deteriorated, and the inhibitor required for the secondary recrystallization was not sufficiently secured, and sufficient secondary recrystallization was not obtained. From the viewpoint of obtaining a high magnetic flux density, which is one of the gist of the present invention, a heating rate of 50 ° C./Hr or higher is desirable.
【００４６】以下、本発明の実施態様を述べる。Ｓｉ：
２．０〜４．８重量％、インヒビター構成元素として、
酸可溶性Ａｌ，Ｍｎ，Ｓ，Ｓｅ，Ｓｂ，Ｐ，Ｂ，Ｓｎ，
Ｂｉ，Ｎｂ，Ｔｉ，Ｍｏ，Ｃｕ等の１種あるいは２種以
上が添加された溶鋼を、通常の工程で、もしくは、連続
鋳造して熱延鋼板あるいは、熱延鋼帯とする。The embodiments of the present invention will be described below. Si:
2.0 to 4.8% by weight, as an inhibitor constituent element,
Acid-soluble Al, Mn, S, Se, Sb, P, B, Sn,
Molten steel to which one or more kinds of Bi, Nb, Ti, Mo, Cu, etc. have been added is formed into a hot rolled steel sheet or a hot rolled steel strip by an ordinary process or continuous casting.
【００４７】この熱延鋼板あるいは、熱延鋼帯は、７５
０℃〜１２００℃の温度域で、３０秒〜３０分間磁束密
度向上のための焼鈍が行われる。続いて、これらの熱延
鋼板あるいは、熱延鋼帯は、冷間圧延される。冷間圧延
は、特公昭４０−１５６４４号公報に開示されているよ
うに最終冷間圧延率８０％以上とする。This hot-rolled steel sheet or hot-rolled steel strip is 75
Annealing for improving the magnetic flux density is performed in a temperature range of 0 ° C to 1200 ° C for 30 seconds to 30 minutes. Subsequently, these hot rolled steel sheets or hot rolled steel strips are cold rolled. The cold rolling is performed at a final cold rolling rate of 80% or more, as disclosed in Japanese Patent Publication No. 40-15644.
【００４８】冷間圧延後の材料は、通常鋼中の炭素を除
去するために湿水雰囲気中で、７５０℃〜９００℃の温
度域で一次再結晶焼鈍される。この時、脱炭、一次再結
晶と共に、鋼板表面には酸化層が形成される。この酸化
層は、湿水雰囲気すなわち水分の入った雰囲気の水分量
の程度（通常、露点で表す）によるが、いわゆる内部酸
化層を形成し鋼板表面から０．１〜６．０μｍの厚さに
なり、ここには、酸化物として、主にＳｉＯ2 が存在す
る。The material after cold rolling is usually subjected to primary recrystallization annealing in a temperature range of 750 ° C. to 900 ° C. in a wet water atmosphere in order to remove carbon in steel. At this time, an oxide layer is formed on the surface of the steel sheet together with decarburization and primary recrystallization. This oxide layer forms a so-called internal oxide layer and has a thickness of 0.1 to 6.0 μm from the surface of the steel sheet, depending on the degree of water content (usually represented by dew point) in a wet water atmosphere, that is, an atmosphere containing water. Therefore, SiO 2 mainly exists as an oxide here.
【００４９】なお一次再結晶焼鈍時形成される酸化物の
酸素量の８０〜９０％以上は、ＳｉＯ2 の形態をとって
いる。一次再結晶後の鋼板、あるいは、鋼帯は、極限の
磁気特性を追求するときは表面の酸化層が除去される。
前記するように若干磁気特性が悪くても良い場合は、こ
の工程は省かれる。この選択は費用と特性の観点からな
される。酸化膜除去方法は、前記の通り物理的及び化学
的方法であるが、一般に酸洗によって行われる。Note that 80 to 90% or more of the oxygen amount of the oxide formed during the primary recrystallization annealing is in the form of SiO 2 . The oxide layer on the surface of the steel sheet or steel strip after primary recrystallization is removed when the ultimate magnetic properties are pursued.
If the magnetic properties may be slightly poor as described above, this step is omitted. This choice is made in terms of cost and characteristics. The oxide film removal method is a physical or chemical method as described above, but is generally performed by pickling.
【００５０】窒化物のインヒビターを使用する場合は、
鋼板表面の酸化層除去に先だってインヒビター強化のた
め、アンモニアによる窒化処理を行うことは磁束密度向
上に極めて有効である。表面の酸化層が除去された一次
再結晶板は、平均粒径が０．５〜１０．０μｍのアルミ
ナ（Ａｌ2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア
（ＺｒＯ2 ）、酸化ストロンチウム（ＳｒＯ）、及びフ
ォルステライト（Ｍｇ2ＳｉＯ4 ）の１種あるいは２種
以上を主成分とする焼鈍分離剤を該鋼板に塗布されて仕
上げ焼鈍炉に入る。If a nitride inhibitor is used,
Nitrogen treatment with ammonia is extremely effective for improving the magnetic flux density in order to strengthen the inhibitor before removing the oxide layer on the steel sheet surface. The primary recrystallized plate from which the oxide layer on the surface has been removed has an average particle diameter of 0.5 to 10.0 μm such as alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO 2 ). ) And forsterite (Mg 2 SiO 4 ), and an annealing separating agent containing at least one of them as a main component are applied to the steel sheet, and the steel sheet enters a finishing annealing furnace.
【００５１】仕上げ焼鈍の昇温時の雰囲気は、中性ある
いは還元性で、窒素分圧調整のためアルゴン、ヘリウム
等の不活性ガスを混合することは何等さしさわりない。
二次再結晶完了後、純化のため１００％水素で高温（約
１２００℃）保持される。仕上げ焼鈍終了後、レーザー
ビーム照射等の磁区細分化処理を行い、さらに張力コー
ティング処理を行う。The atmosphere at the time of raising the temperature of the finish annealing is neutral or reducing, and mixing of an inert gas such as argon or helium for adjusting the nitrogen partial pressure does not matter at all.
After the completion of the secondary recrystallization, it is kept at a high temperature (about 1200 ° C.) with 100% hydrogen for purification. After finishing annealing, magnetic domain subdivision processing such as laser beam irradiation is performed, and tension coating processing is further performed.
【００５２】[0052]
実施例１ Ｓｉ：３．３重量％、酸可溶性Ａｌ：０．０２５重量
％、Ｎ：０．００９重量％、Ｍｎ：０．０７重量％、
Ｓ：０．０１５量％、Ｃ：０．０８重量％、Ｓｅ：０．
０１５量％、Ｓｎ：０．１３重量％、Ｃｕ：０．０７重
量％、残部Ｆｅ及び不可避的不純物からなる珪素熱延鋼
帯を１１２０℃で２分間焼鈍した後、冷間圧延し、０．
２０mm厚とした。これらの冷延板を、脱炭を兼ねるため
に湿水雰囲気（露点：６５℃）とした焼鈍炉で８５０℃
で２分間焼鈍し、一次再結晶させた。Example 1 Si: 3.3 wt%, acid-soluble Al: 0.025 wt%, N: 0.009 wt%, Mn: 0.07 wt%,
S: 0.015% by weight, C: 0.08% by weight, Se: 0.
A hot-rolled silicon steel strip consisting of 015% by weight, Sn: 0.13% by weight, Cu: 0.07% by weight, balance Fe and unavoidable impurities was annealed at 1120 ° C. for 2 minutes, cold-rolled,
It was 20 mm thick. These cold-rolled sheets were heated at 850 ° C. in an annealing furnace in a wet water atmosphere (dew point: 65 ° C.) to also serve as decarburization.
It was annealed for 2 minutes, and primary recrystallization was performed.
【００５３】その後、そのまま、及び０．５％フッ
酸−５％硫酸混合溶液で酸洗した。２種の材料に平均粒
径が４．０μｍのＡｌ2 Ｏ3 水スラリー状態で塗布し
た、また比較のため酸洗しないで、ＭｇＯを主体とす
る焼鈍分離剤を水スラリー状態で塗布した。Then, it was pickled as it was and with a mixed solution of 0.5% hydrofluoric acid and 5% sulfuric acid. Two kinds of materials were applied in an Al 2 O 3 water slurry state having an average particle diameter of 4.0 μm, and for comparison, an annealing separator mainly composed of MgO was applied in a water slurry state without pickling.
【００５４】これら３種の材料を、１２００℃まで、２
５％Ｎ2 −７５％Ｈ2 雰囲気で、１５℃／Hrの昇温速度
を保ちながら昇温し、１２００℃到達後、１００％水素
とし、該温度で２０時間保持した。仕上げ焼鈍終了後、
レーザービームを照射し、リン酸−クロム酸系の張力コ
ーティング処理を行った。得られた製品の特性は、表１
の通りである。These three kinds of materials are heated to 1200 ° C.
The temperature was raised in a 5% N 2 -75% H 2 atmosphere while maintaining the temperature rising rate of 15 ° C./Hr, and after reaching 1200 ° C., 100% hydrogen was obtained and the temperature was maintained for 20 hours. After finishing annealing,
Irradiation with a laser beam was performed for phosphoric acid-chromic acid-based tension coating treatment. The characteristics of the obtained product are shown in Table 1.
Is the street.
【００５５】[0055]
【表１】 [Table 1]
【００５６】実施例２ Ｓｉ：３．２重量％、酸可溶性Ａｌ：０．０２９重量
％、Ｎ：０．００８重量％、Ｍｎ：０．１３重量％、
Ｓ：０．００７重量％、Ｃ：０．０５重量％、残部Ｆｅ
及び不可避的不純物からなる珪素熱延鋼帯を１１００℃
で２分間焼鈍した後、冷間圧延し、０．１８mm厚とし
た。これらの冷延板を脱炭を兼ねるために湿水雰囲気と
した焼鈍炉で８２０℃で２分間焼鈍し、一次再結晶させ
た。次に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、インヒビターを強化した。Example 2 Si: 3.2% by weight, acid-soluble Al: 0.029% by weight, N: 0.008% by weight, Mn: 0.13% by weight,
S: 0.007 wt%, C: 0.05 wt%, balance Fe
And hot-rolled silicon steel strip consisting of inevitable impurities at 1100 ° C
After annealing for 2 minutes, it was cold rolled to a thickness of 0.18 mm. These cold-rolled sheets were annealed at 820 ° C. for 2 minutes in an annealing furnace in a wet water atmosphere for double decarburization, and primary recrystallization was performed. Next, in order to stabilize the secondary recrystallization, nitriding treatment was performed in an ammonia atmosphere to adjust the total nitrogen amount to 190 ppm and strengthen the inhibitor.
【００５７】その後、フッ酸の混合した硫酸で鋼板表
面に生成している酸化層を除去し、平均粒径２．０μｍ
のＡｌ2 Ｏ3 を水スラリー状態で焼鈍分離剤として塗布
した、そのまま、平均粒径２．０μｍのＡｌ2 Ｏ3 を
水スラリー状態で焼鈍分離剤として塗布した、そのま
ま、ＭｇＯを主体とする焼鈍分離剤を水スラリー状態で
塗布した。After that, the oxide layer formed on the surface of the steel sheet was removed with sulfuric acid mixed with hydrofluoric acid, and the average particle size was 2.0 μm.
Al 2 O 3 in the form of an aqueous slurry was applied as an annealing separator, and as it was, Al 2 O 3 having an average particle size of 2.0 μm was applied in the form of an aqueous slurry as an annealing separator. The separating agent was applied as a water slurry.
【００５８】これら３種の材料を、１２００℃まで、２
５％Ｎ2 −７５％Ｈ2 雰囲気で、３０℃／Hrの昇温速度
を保ちながら昇温し、１２００℃到達後、１００℃水素
とし、該温度で２０時間保持した。仕上げ焼鈍終了後、
レーザービームを照射し、リン酸−クロム酸系の張力コ
ーティング処理を行った。得られた製品の特性は、表２
の通りである。These three kinds of materials were heated to 1200 ° C., and 2
The temperature was raised in a 5% N 2 -75% H 2 atmosphere while maintaining the temperature rising rate of 30 ° C./Hr, and after reaching 1200 ° C., hydrogen was set to 100 ° C. and the temperature was maintained for 20 hours. After finishing annealing,
Irradiation with a laser beam was performed for phosphoric acid-chromic acid-based tension coating treatment. The characteristics of the obtained product are shown in Table 2.
Is the street.
【００５９】[0059]
【表２】 [Table 2]
【００６０】実施例３ Ｓｉ：３．２重量％、酸可溶性Ａｌ：０．０３０重量
％、Ｎ：０．００８重量％、Ｍｎ：０．１３重量％、
Ｓ：０．００７重量％、Ｃ：０．０５重量％、残部Ｆｅ
及び不可避的不純物からなる珪素熱延鋼帯を１１００℃
で２分間焼鈍した後、冷間圧延し、０．１５mm厚とし
た。Example 3 Si: 3.2% by weight, acid-soluble Al: 0.030% by weight, N: 0.008% by weight, Mn: 0.13% by weight,
S: 0.007 wt%, C: 0.05 wt%, balance Fe
And hot-rolled silicon steel strip consisting of inevitable impurities at 1100 ° C
After annealing for 2 minutes, it was cold rolled to a thickness of 0.15 mm.
【００６１】これらの冷延板を脱炭を兼ねるために湿水
雰囲気とした焼鈍炉で８２０℃で２分間焼鈍し、一次再
結晶させた。次に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２００
ppm とし、インヒビターを強化した。These cold-rolled sheets were annealed at 820 ° C. for 2 minutes in an annealing furnace in a wet water atmosphere in order to also serve as decarburization, and primary recrystallization was performed. Next, in order to stabilize the secondary recrystallization, nitriding treatment is performed in an ammonia atmosphere, and the total nitrogen amount is reduced to 200
ppm to enhance the inhibitor.
【００６２】その後、フッ酸の混合した硫酸で鋼板表面
に生成している酸化層を除去し、平均粒径２．０μｍ
のＡｌ2 Ｏ3 を水スラリー状態で焼鈍分離剤とし、１２
００℃まで、１００％Ｈ2 雰囲気で、平均粒径２．０
μｍのＡｌ2 Ｏ3 を水スラリー状態で焼鈍分離剤とし、
１２００℃まで、５％Ｎ2 −９５％Ｈ2 雰囲気で、平
均粒径２．０μｍのＡｌ2 Ｏ3 を水スラリー状態で焼鈍
分離剤とし、１２００℃まで、７５％Ｎ2 −２５％Ｈ2
雰囲気で、さらに比較のためＭｇＯを水スラリー状態
で焼鈍分離剤とし、１２００℃まで、５％Ｎ2 −９５％
Ｈ2 雰囲気で、３０℃／Hrの昇温速度を保ちながら昇温
し、１２００℃到達後、１００％水素とし、該温度で２
０時間保持した。仕上げ焼鈍終了後、レーザービームを
照射し、リン酸−クロム酸系の張力コーティング処理を
行った。得られた製品の特性は、表３の通りである。After that, the oxide layer formed on the surface of the steel sheet was removed with sulfuric acid mixed with hydrofluoric acid, and the average particle size was 2.0 μm.
Al 2 O 3 as an annealing separator in a water slurry state,
Up to 00 ° C, 100% H 2 atmosphere, average particle size 2.0
μm Al 2 O 3 as an annealing separator in a water slurry state,
To 1200 ° C., in 5% N 2 -95% H 2 atmosphere, the Al 2 O 3 having an average particle size of 2.0μm and annealing separator in water slurry, to 1200 ℃, 75% N 2 -25 % H 2
In an atmosphere, for comparison, MgO was used as an annealing separator in a water slurry state, and up to 1200 ° C., 5% N 2 -95%
In the H 2 atmosphere, the temperature was raised while maintaining the temperature rising rate of 30 ° C./Hr, and after reaching 1200 ° C., 100% hydrogen was added and the temperature was raised to 2
Hold for 0 hours. After finishing annealing, a laser beam was irradiated to perform a phosphoric acid-chromic acid tension coating process. The characteristics of the obtained product are as shown in Table 3.
【００６３】[0063]
【表３】 [Table 3]
【００６４】実施例４ 実施例３における一次再結晶板を、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２１０ppm とし、インヒビターを強化した。Example 4 The primary recrystallized plate of Example 3 was subjected to a nitriding treatment in an ammonia atmosphere in order to stabilize secondary recrystallization,
The total nitrogen content was 210 ppm and the inhibitor was strengthened.
【００６５】その後フッ酸の混合した硫酸で鋼板表面に
生成している酸化層を除去し、焼鈍分離剤として、平
均粒径２．０μｍのアルミナ（Ａｌ2 Ｏ3 ）を静電塗布
し、１２００℃まで、１００％Ｈ2 雰囲気で、焼鈍分
離剤として、平均粒径２．０μｍのアルミナ（Ａｌ2 Ｏ
3 ）を静電塗布し、１２００℃まで、５％Ｎ2 −９５％
Ｈ2 雰囲気で、焼鈍分離剤として、平均粒径２．０μ
ｍのアルミナ（Ａｌ2Ｏ3 を静電塗布し、１２００℃ま
で、７５％Ｎ2 −２５％Ｈ2 雰囲気で、さらに比較のた
めＭｇＯを水スラリー状態で焼鈍分離剤とし、１２０
０℃まで、５％Ｎ2 −９５％Ｈ2 雰囲気で、３０℃／Hr
の昇温速度を保ちながら昇温し、１２００℃到達後、１
００％水素とし、該温度で２０時間保持した。After that, the oxide layer formed on the surface of the steel sheet was removed with sulfuric acid mixed with hydrofluoric acid, and alumina (Al 2 O 3 ) having an average particle size of 2.0 μm was electrostatically applied as an annealing separator, and 1200 As an annealing separator in an atmosphere of 100% H 2 up to ℃, alumina having an average particle size of 2.0 μm (Al 2 O
3 ) is electrostatically applied, up to 1200 ° C, 5% N 2 -95%
Average particle size of 2.0μ as annealing separator in H 2 atmosphere
m of alumina (Al 2 O 3 was electrostatically coated, and up to 1200 ° C. in an atmosphere of 75% N 2 -25% H 2 and, for comparison, MgO was used as an annealing separator in a water slurry state.
Up to 0 ° C, 5% N 2 -95% H 2 atmosphere, 30 ° C / Hr
The temperature is raised while maintaining the temperature rising rate of
It was set to 00% hydrogen and kept at this temperature for 20 hours.
【００６６】仕上げ焼鈍終了後、レーザービームを照射
し、リン酸−クロム酸系の張力コーティング処理を行っ
た。得られた製品の特性は、表４の通りである。After the finish annealing, a laser beam was irradiated to perform a phosphoric acid-chromic acid tension coating process. The characteristics of the obtained product are shown in Table 4.
【００６７】[0067]
【表４】 [Table 4]
【００６８】実施例５ Ｓｉ：３．２重量％、酸可溶性Ａｌ：０．０３０重量
％、：０．００７重量％、Ｍｎ：０．１４重量％、Ｓ：
０．００７重量％、Ｃ：０．０５重量％、残部Ｆｅ及び
不可避的不純物からなる珪素熱延鋼帯を１１００℃で２
分間焼鈍した後、冷間圧延し、０．１５mm厚とした。Example 5 Si: 3.2% by weight, acid-soluble Al: 0.030% by weight ,: 0.007% by weight, Mn: 0.14% by weight, S:
A hot-rolled silicon steel strip composed of 0.007% by weight, C: 0.05% by weight, the balance Fe and unavoidable impurities at 1100 ° C.
After annealing for 1 minute, it was cold rolled to a thickness of 0.15 mm.
【００６９】これらの冷延板を脱炭を兼ねるために湿水
雰囲気とした焼鈍炉で８５０℃で２分間焼鈍し、一次再
結晶させた。次に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２００
ppm とし、インヒビターを強化した。These cold-rolled sheets were annealed at 850 ° C. for 2 minutes in an annealing furnace in a wet water atmosphere in order to also serve as decarburization, and primary recrystallization was performed. Next, in order to stabilize the secondary recrystallization, nitriding treatment is performed in an ammonia atmosphere, and the total nitrogen amount is reduced to 200
ppm to enhance the inhibitor.
【００７０】その後、フッ酸の混合した硫酸で鋼板表面
に生成している酸化層を除去し、平均粒径０．３μｍ
のアルミナ（Ａｌ2 Ｏ3 ）、平均粒径０．５μｍのア
ルミナ（Ａｌ2 Ｏ3 ）、平均粒径３．０μｍのアルミ
ナ（Ａｌ2 Ｏ3 ）、平均粒径１０．０μｍのアルミナ
（Ａｌ2 Ｏ3 ）、平均粒径１４．９μｍのアルミナ
（Ａｌ2 Ｏ3 ）、平均粒径３５μｍのアルミナ（Ａｌ
2 Ｏ3 ）を水スラリー状態で焼鈍分離剤として塗布し
た。After that, the oxide layer formed on the surface of the steel sheet was removed with sulfuric acid mixed with hydrofluoric acid, and the average particle size was 0.3 μm.
Alumina (Al 2 O 3 ), average particle size 0.5 μm alumina (Al 2 O 3 ), average particle size 3.0 μm alumina (Al 2 O 3 ), average particle size 10.0 μm alumina (Al 2 O 3 ), alumina having an average particle size of 14.9 μm (Al 2 O 3 ), alumina having an average particle size of 35 μm (Al
2 O 3 ) was applied as an annealing separator in a water slurry state.
【００７１】この材料を、１２００℃まで、７５％Ｎ2
−２５％Ｈ2 雰囲気で、３０℃／Hrの昇温速度を保ちな
がら昇温し、１２００℃到達後、１００％水素とし、該
温度で２０時間保持した。仕上げ焼鈍終了後、レーザー
ビームを照射し、リン酸−クロム酸系の張力コーティン
グ処理を行った。得られた製品の特性は、表５の通りで
ある。This material was treated with 75% N 2 up to 1200 ° C.
The temperature was raised in a -25% H 2 atmosphere while maintaining the temperature rising rate of 30 ° C./Hr, and after reaching 1200 ° C., 100% hydrogen was obtained and the temperature was maintained for 20 hours. After finishing annealing, a laser beam was irradiated to perform a phosphoric acid-chromic acid tension coating process. The characteristics of the obtained product are as shown in Table 5.
【００７２】[0072]
【表５】 [Table 5]
【００７３】実施例６ 実施例５において、冷間圧延した鋼板を脱炭を兼ねるた
めに湿水雰囲気とした焼鈍炉で８４０℃で２分間焼鈍
し、一次再結晶させた。次に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２１０ppm とし、インヒビターを強化した。その
後、フッ酸の混合した硫酸で鋼板表面に生成している酸
化層を除去し、平均粒径０．３μｍのアルミナ（Ａｌ
2 Ｏ3 ）、平均粒径３．０μｍのアルミナ（Ａｌ2 Ｏ
3 ）、平均粒径３．０μｍのシリカ、平均粒径３．
３μｍジルコニア、平均粒径３．０μｍの酸化ストロ
ンチウム、平均粒径３．０μｍのフォルステライトを
それぞれ該鋼板に焼鈍分離剤として静電塗布した。Example 6 In Example 5, the cold-rolled steel sheet was annealed at 840 ° C. for 2 minutes in an annealing furnace in a wet water atmosphere to also serve as decarburization, and primary recrystallization was performed. Next, in order to stabilize the secondary recrystallization, nitriding treatment was performed in an ammonia atmosphere so that the total nitrogen amount was 210 ppm, and the inhibitor was strengthened. After that, the oxide layer formed on the surface of the steel sheet was removed with sulfuric acid mixed with hydrofluoric acid, and alumina (Al
2 O 3 ) and alumina having an average particle size of 3.0 μm (Al 2 O 3
3 ), silica having an average particle size of 3.0 μm, and an average particle size of 3.
3 μm zirconia, strontium oxide having an average particle size of 3.0 μm, and forsterite having an average particle size of 3.0 μm were electrostatically applied to the steel sheets as an annealing separator.
【００７４】この材料を、１２００℃まで、７５％Ｎ2
−２５％Ｈ2 雰囲気で、３０℃／Hrの昇温速度を保ちな
がら昇温し、１２００℃到達後、１００％水素とし、該
温度で２０時間保持した。仕上げ焼鈍終了後、レーザー
ビームを照射し、リン酸−クロム酸系の張力コーティン
グ処理を行った。得られた製品の特性は、表６の通りで
ある。This material was treated with 75% N 2 up to 1200 ° C.
The temperature was raised in a -25% H 2 atmosphere while maintaining the temperature rising rate of 30 ° C./Hr, and after reaching 1200 ° C., 100% hydrogen was obtained and the temperature was maintained for 20 hours. After finishing annealing, a laser beam was irradiated to perform a phosphoric acid-chromic acid tension coating process. The characteristics of the obtained product are as shown in Table 6.
【００７５】[0075]
【図６】 [Figure 6]
【００７６】[0076]
【発明の効果】本発明により、磁束密度が高く、磁気特
性を阻害する要因である鋼板表面の凹凸の小さい（鏡面
である）方向性電磁鋼板が容易に得られ、レーザービー
ム照射処理等の磁区細分化、張力コーティング処理によ
り極めて低鉄損の磁気材料が提供された。この方向性電
磁鋼板の製造に当たっては鋼板の鏡面化処理が通常の仕
上げ焼鈍炉中で行われるため、極めて容易であり、工業
上の価値は絶大である。According to the present invention, a grain-oriented electrical steel sheet having a high magnetic flux density and small irregularities on the surface of the steel sheet (which is a mirror surface) which is a factor that obstructs magnetic properties can be easily obtained, and magnetic domains for laser beam irradiation treatment or the like can be obtained. The subdivided, tension-coated treatment provided a magnetic material with extremely low iron loss. In the production of this grain-oriented electrical steel sheet, mirror finishing of the steel sheet is carried out in a normal finish annealing furnace, so that it is extremely easy and its industrial value is enormous.
【図１】仕上げ焼鈍中の鋼板のインヒビター（酸可溶性
Ａｌ）の変化を示す図表である。FIG. 1 is a chart showing changes in an inhibitor (acid-soluble Al) of a steel sheet during finish annealing.
【図２】酸可溶性Ａｌを含有せずＳを含有する鋼板の仕
上げ焼鈍中の鋼板のＳの変化を示す図表である。FIG. 2 is a chart showing changes in S of a steel sheet during finish annealing of a steel sheet containing S without containing acid-soluble Al.
フロントページの続き (72)発明者 牛神 義行 富津市新富20−１ 新日本製鐵株式会社技 術開発本部内Front Page Continuation (72) Inventor Yoshiyuki Ushigami 20-1 Shintomi, Futtsu City Nippon Steel Corporation Technical Development Division
Claims (12)
中間焼鈍をはさむ２回以上の冷間圧延によって最終板厚
とし、次いで一次再結晶焼鈍を施した後焼鈍分離剤を塗
布し、仕上げ焼鈍を施す方向性珪素鋼板の製造方法にお
いて、一次再結晶焼鈍後、平均粒径が０．５〜１０．０
μｍのアルミナ（Ａｌ2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、
ジルコニア（ＺｒＯ2 ）、酸化ストロンチウム（Ｓｒ
Ｏ）、及びフォルステライト（Ｍｇ2 ＳｉＯ4 ）の１種
あるいは２種以上を主成分とする焼鈍分離剤を該鋼板に
塗布し、次いで中性あるいは還元性雰囲気で仕上げ焼鈍
を施すことを特徴とする方向性珪素鋼板の製造方法。1. A hot-rolled silicon steel strip is cold-rolled once or twice with intermediate annealing to obtain a final plate thickness, then subjected to primary recrystallization annealing and then applied with an annealing separator. In the method for producing a grain-oriented silicon steel sheet subjected to finish annealing, the average grain size is 0.5 to 10.0 after primary recrystallization annealing.
μm alumina (Al 2 O 3 ), silica (SiO 2 ),
Zirconia (ZrO 2 ), strontium oxide (Sr
O), and forsterite (Mg 2 SiO 4 ), an annealing separator containing at least one of these as the main component is applied to the steel sheet, and then finish annealing is performed in a neutral or reducing atmosphere. A method of manufacturing a grain-oriented silicon steel sheet.
た鋼板表面の酸化膜を除去し、次いで、平均粒径が０．
５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ3 ）、シリカ
（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ストロン
チウム（ＳｒＯ）、及びフォルステライト（Ｍｇ2 Ｓｉ
Ｏ4 ）の１種あるいは２種以上を主成分とする焼鈍分離
剤を該鋼板に塗布し、次いで中性あるいは還元性雰囲気
で仕上げ焼鈍を施すことを特徴とする請求項１記載の方
向性珪素鋼板の製造方法。2. After the primary recrystallization annealing, the oxide film on the surface of the steel sheet produced in the annealing step is removed, and then the average grain size is reduced to 0.
5 to 10.0 μm alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 Si).
2. The directional silicon according to claim 1, wherein an annealing separator containing at least one of O 4 ) as a main component is applied to the steel sheet, and then finish annealing is performed in a neutral or reducing atmosphere. Steel plate manufacturing method.
を、１回または中間焼鈍をはさむ２回以上の冷間圧延に
よって、所定の板厚とし、次いで一次再結晶焼鈍を行っ
た後焼鈍分離剤を塗布し、仕上げ焼鈍を施す方向性珪素
鋼板の製造方法において、一次再結晶焼鈍後、平均粒径
が０．５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ3 ）、シ
リカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化スト
ロンチウム（ＳｒＯ）、及びフォルステライト（Ｍｇ2
ＳｉＯ4 ）の１種あるいは２種以上を主成分とする焼鈍
分離剤を該鋼板に塗布し、次いで中性あるいは還元性雰
囲気で仕上げ焼鈍を施すことを特徴とする方向性珪素鋼
板の製造方法。3. Si: 2.0 to 4.8% by weight, acid-soluble Al: 0.008 to 0.05% by weight, N ≦ 0.010% by weight, balance: silicon heat composed of Fe and unavoidable impurities The rolled steel strip is made to have a predetermined thickness by cold rolling once or twice or more with intermediate annealing, and then primary recrystallization annealing is performed, and then an annealing separator is applied, and finish annealing is performed. In the method for producing a steel sheet, after primary recrystallization annealing, alumina (Al 2 O 3 ) having an average particle size of 0.5 to 10.0 μm, silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), And forsterite (Mg 2
A method for producing a grain-oriented silicon steel sheet, which comprises applying an annealing separator containing at least one of SiO 4 ) as a main component to the steel sheet, and then performing finish annealing in a neutral or reducing atmosphere.
た鋼板表面の酸化膜を除去し、次いで、平均粒径が０．
５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ3 ）、シリカ
（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ストロン
チウム（ＳｒＯ）、及びフォルステライト（Ｍｇ2 Ｓｉ
Ｏ4 ）の１種あるいは２種以上を主成分とする焼鈍分離
剤を該鋼板に塗布し、次いで中性あるいは還元性雰囲気
で仕上げ焼鈍を施すことを特徴とする請求項３記載の方
向性珪素鋼板の製造方法。4. After the primary recrystallization annealing, the oxide film on the surface of the steel sheet formed in the annealing step is removed, and then the average grain size is reduced to 0.
5 to 10.0 μm alumina (Al 2 O 3 ), silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 Si).
4. The directional silicon according to claim 3, wherein an annealing separator having at least one of O4) as a main component is applied to the steel sheet, and then finish annealing is performed in a neutral or reducing atmosphere. Steel plate manufacturing method.
中間焼鈍をはさむ２回以上の冷間圧延によって、所定の
板厚とし、次いで一次再結晶焼鈍を施した後焼鈍分離剤
を塗布し、仕上げ焼鈍を施す方向性珪素鋼板の製造方法
において、一次再結晶焼鈍後、アンモニアガスを含む雰
囲気中で窒化処理し、次いで平均粒径が０．５〜１０．
０μｍのアルミナ（Ａｌ2 Ｏ3 ）、シリカ（Ｓｉ
Ｏ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ストロンチウム
（ＳｒＯ）、及びフォルステライト（Ｍｇ2 ＳｉＯ4 ）
の１種あるいは２種以上を主成分とする焼鈍分離剤を該
鋼板に塗布し、次いで、中性あるいは、還元性雰囲気で
仕上げ焼鈍を施すことを特徴とする方向性珪素鋼板の製
造方法。5. A hot-rolled silicon steel strip is cold rolled one or more times with intermediate annealing to a predetermined plate thickness and then subjected to primary recrystallization annealing, followed by an annealing separator. In the method for producing a grain-oriented silicon steel sheet which is applied and subjected to finish annealing, after primary recrystallization annealing, nitriding treatment is performed in an atmosphere containing ammonia gas, and then the average grain size is 0.5 to 10.
0 μm alumina (Al 2 O 3 ), silica (Si
O 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg 2 SiO 4 ).
1. A method for producing a grain-oriented silicon steel sheet, which comprises applying the annealing separator containing at least one of the above as a main component to the steel sheet, and then performing finish annealing in a neutral or reducing atmosphere.
む雰囲気中で鋼板を窒化処理した後、一次再結晶焼鈍工
程で生じる鋼板表面の酸化膜を除去し、次いで、平均粒
径が０．５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ3 ）、
シリカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ス
トロンチウム（ＳｒＯ）、及びフォルステライト（Ｍｇ
2 ＳｉＯ4 ）の１種あるいは２種以上を主成分とする焼
鈍分離剤を該鋼板に塗布し、次いで、中性あるいは、還
元性雰囲気で仕上げ焼鈍を施すことを特徴とする請求項
５記載の方向性珪素鋼板の製造方法。6. After the primary recrystallization annealing, the steel sheet is nitrided in an atmosphere containing ammonia gas, the oxide film on the surface of the steel sheet generated in the primary recrystallization annealing step is removed, and then the average grain size is 0.5. ~ 10.0 μm alumina (Al 2 O 3 ),
Silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg)
6. An annealing separator containing at least one of ( 2 SiO 4 ) as a main component is applied to the steel sheet, and then finish annealing is performed in a neutral or reducing atmosphere. Method for manufacturing grain-oriented silicon steel sheet.
Ａｌ：０．００８〜０．０５重量％、Ｎ≦０．０１０重
量％、残部：Ｆｅ及び不可避的不純物からなる珪素熱延
鋼帯を、１回または中間焼鈍をはさむ２回以上の冷間圧
延によって、所定の板厚とし、次いで一次再結晶焼鈍を
施した後焼鈍分離剤を塗布し、仕上げ焼鈍を施す方向性
珪素鋼板の製造方法において、一次再結晶焼鈍後、アン
モニアガスを含む雰囲気中で窒化処理し、次いで、平均
粒径が０．５〜１０．０μｍのアルミナ（Ａｌ
2 Ｏ3 ）、シリカ（ＳｉＯ2 ）、ジルコニア（Ｚｒ
Ｏ2 ）、酸化ストロンチウム（ＳｒＯ）、及びフォルス
テライト（Ｍｇ2 ＳｉＯ4 ）の１種あるいは２種以上を
主成分とする焼鈍分離剤を該鋼板に塗布し、次いで中性
あるいは還元性雰囲気で仕上げ焼鈍を施すことを特徴と
する方向性珪素鋼板の製造方法。7. Si: 2.0 to 4.8% by weight, acid-soluble Al: 0.008 to 0.05% by weight, N ≦ 0.010% by weight, balance: silicon heat composed of Fe and unavoidable impurities Directional silicon in which a steel strip is made to have a predetermined thickness by cold rolling once or twice or more with intermediate annealing, then primary recrystallization annealing is applied, and then an annealing separator is applied, and finish annealing is performed. In the method for manufacturing a steel sheet, after primary recrystallization annealing, nitriding treatment is performed in an atmosphere containing ammonia gas, and then alumina (Al (Al) having an average particle size of 0.5 to 10.0 μm is used.
2 O 3 ), silica (SiO 2 ), zirconia (Zr
O 2 ), strontium oxide (SrO), and forsterite (Mg 2 SiO 4 ) are applied to the steel sheet with an annealing separating agent as a main component, and then finished in a neutral or reducing atmosphere. A method for manufacturing a grain-oriented silicon steel sheet, which comprises performing annealing.
む雰囲気中で窒化処理し、次いで、一次再結晶焼鈍工程
で生成した鋼板表面の酸化膜を除去し、次いで、平均粒
径が０．５〜１０．０μｍのアルミナ（Ａｌ2 Ｏ3 ）、
シリカ（ＳｉＯ2 ）、ジルコニア（ＺｒＯ2 ）、酸化ス
トロンチウム（ＳｒＯ）、及びフォルステライト（Ｍｇ
2 ＳｉＯ4 ）の１種あるいは２種以上を主成分とする焼
鈍分離剤を該鋼板に塗布し、次いで、中性あるいは、還
元性雰囲気で仕上げ焼鈍を施すことを特徴とする請求項
７記載の方向性珪素鋼板の製造方法。8. After the primary recrystallization annealing, nitriding is performed in an atmosphere containing ammonia gas, and then the oxide film on the surface of the steel sheet produced in the primary recrystallization annealing step is removed, and then the average grain size is 0.5. ~ 10.0 μm alumina (Al 2 O 3 ),
Silica (SiO 2 ), zirconia (ZrO 2 ), strontium oxide (SrO), and forsterite (Mg)
8. An annealing separator containing at least one of ( 2 SiO 4 ) as a main component is applied to the steel sheet, and then finish annealing is performed in a neutral or reducing atmosphere. Method for manufacturing grain-oriented silicon steel sheet.
の酸化膜を除去する手段が酸洗であることを特徴とする
請求項２，４，６あるいは８いずれかに記載の方向性珪
素鋼板の製造方法。9. The grain-oriented silicon steel sheet according to claim 2, wherein the means for removing the oxide film on the surface of the steel sheet produced in the primary recrystallization annealing step is pickling. Manufacturing method.
面の酸化膜を除去する手段が鋼板をフッ酸を含む酸洗溶
液によって酸洗することを特徴とする請求項２，４，６
あるいは８いずれかに記載の方向性珪素鋼板の製造方
法。10. The steel sheet is pickled with a pickling solution containing hydrofluoric acid as a means for removing an oxide film formed on the surface of the steel sheet in the primary recrystallization annealing step.
Alternatively, the method for manufacturing the grain-oriented silicon steel sheet according to any one of 8 to 8.
ルミナ（Ａｌ2 Ｏ3）を主成分とする焼鈍分離剤の鋼板
への塗布が該焼鈍分離剤の水スラリー形態であることを
特徴とする請求項１〜１０いずれかに記載の方向性珪素
鋼板の製造方法。11. The method for applying an annealing separator, which comprises alumina (Al 2 O 3 ) having an average particle diameter of 0.5 to 10.0 μm as a main component, to a steel sheet in the form of a water slurry of the annealing separator. The method for manufacturing a grain-oriented silicon steel sheet according to any one of claims 1 to 10.
気中のＮ2 含有量を５％以上とすることを特徴とする請
求項１〜１１いずれかに記載の方向性珪素鋼板の製造方
法。12. The method for producing a grain-oriented silicon steel sheet according to claim 1, wherein the N 2 content in the atmosphere during the temperature rise in the finish annealing step is 5% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5032299A JPH06100927A (en) | 1992-08-05 | 1993-02-22 | Production of grain-oriented silicon steel sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20922292 | 1992-08-05 | ||
| JP4-209222 | 1992-08-05 | ||
| JP5032299A JPH06100927A (en) | 1992-08-05 | 1993-02-22 | Production of grain-oriented silicon steel sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06100927A true JPH06100927A (en) | 1994-04-12 |
Family
ID=26370843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5032299A Pending JPH06100927A (en) | 1992-08-05 | 1993-02-22 | Production of grain-oriented silicon steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06100927A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS563414A (en) * | 1979-06-22 | 1981-01-14 | Mitsubishi Electric Corp | Sound recorder/reproducer |
| JPH02107722A (en) * | 1988-10-18 | 1990-04-19 | Nippon Steel Corp | Production of grain-oriented electrical steel easy to punch and having metallic luster |
| JPH04259329A (en) * | 1991-02-12 | 1992-09-14 | Sumitomo Metal Ind Ltd | Production of grain-oriented silicon steel sheet excellent in blankability |
-
1993
- 1993-02-22 JP JP5032299A patent/JPH06100927A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS563414A (en) * | 1979-06-22 | 1981-01-14 | Mitsubishi Electric Corp | Sound recorder/reproducer |
| JPH02107722A (en) * | 1988-10-18 | 1990-04-19 | Nippon Steel Corp | Production of grain-oriented electrical steel easy to punch and having metallic luster |
| JPH04259329A (en) * | 1991-02-12 | 1992-09-14 | Sumitomo Metal Ind Ltd | Production of grain-oriented silicon steel sheet excellent in blankability |
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