JPS624881A - Formation of glass film of grain-oriented silicon steel sheet - Google Patents

Formation of glass film of grain-oriented silicon steel sheet

Info

Publication number
JPS624881A
JPS624881A JP14380385A JP14380385A JPS624881A JP S624881 A JPS624881 A JP S624881A JP 14380385 A JP14380385 A JP 14380385A JP 14380385 A JP14380385 A JP 14380385A JP S624881 A JPS624881 A JP S624881A
Authority
JP
Japan
Prior art keywords
steel sheet
annealing
grain
glass film
oriented silicon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP14380385A
Other languages
Japanese (ja)
Other versions
JPS633025B2 (en
Inventor
Masayoshi Mizuguchi
水口 政義
Tadashi Imai
忠 今井
Yozo Suga
菅 洋三
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Priority to JP14380385A priority Critical patent/JPS624881A/en
Publication of JPS624881A publication Critical patent/JPS624881A/en
Publication of JPS633025B2 publication Critical patent/JPS633025B2/ja
Granted legal-status Critical Current

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  • Manufacturing Of Steel Electrode Plates (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

PURPOSE:To form a glass film having fine appearance and superior adhesion on a grain-oriented silicon steel sheet by adding silicon nitride to an MgO-base protective coating material for annealing, applying the coating material to the steel sheet having sub-scale contg. SiO2 formed on the surface by decarburization annealing and subjecting the steel sheet to finish annealing. CONSTITUTION:A grain-oriented silicon steel sheet is cold rolled to a prescribed thickness and subjected to decarburization annealing to form sub-scale contg. SiO2 on the surface of the steel sheet. Silicon nitride is added to a magnesium oxide-base protective coating material for annealing, the coating material is applied to the subscale and the steel sheet is subjected to finish annealing at 900-1,100 deg.C to form a forsterite-base glass film.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は方向性珪素鋼板のグラス皮膜形成方法に係わシ
、外観、密着性などの皮膜特性のすぐれたグラス皮膜の
形成方法に関する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for forming a glass film on a grain-oriented silicon steel sheet, and more particularly, to a method for forming a glass film with excellent film properties such as appearance and adhesion.

(従来の技術) 方向性珪素鋼板のグラス皮膜形成方法として、所望の板
厚に冷間圧延したのち、湿潤雰囲気中で例えば700〜
900℃の温度範囲で脱炭し、その鋼板の表面K 5I
O2’e含むサブスケールを生成させ、次いでMgOを
主成分とする焼鈍分離剤を水に溶解してスラリー状とし
、サブスケールが形成された鋼板表面に塗付し、コイル
状に巻き取って高温仕上焼鈍を施すことによジグラス皮
膜(別名フォルステライト皮膜ともいう。)を形成させ
る方法が知られている。一般に焼鈍分離剤は主としてM
gO’i主成分とし水に懸濁して鋼板にスラリー状で塗
付するが、その塗膜が乾燥状態では剥離を生じない充分
な付着力を示すMgOは前記の懸濁時に一部が水利反応
を生じ、水酸化マグネシウムに下記(1)式に示すよう
に変化する。
(Prior art) As a method for forming a glass film on a grain-oriented silicon steel sheet, the sheet is cold-rolled to a desired thickness and then rolled to a temperature of, for example, 700 to
Decarburized in a temperature range of 900℃, the surface of the steel plate K 5I
Subscale containing O2'e is generated, and then an annealing separator mainly composed of MgO is dissolved in water to form a slurry, applied to the surface of the steel plate on which subscale has been formed, and wound into a coil to heat the slurry at high temperature. A method is known in which a diglas film (also referred to as a forsterite film) is formed by final annealing. Generally, the annealing separator is mainly M
MgO, which is the main component of gO'i, is suspended in water and applied to a steel plate in the form of a slurry, but the coating film shows sufficient adhesion to prevent peeling when dry. is produced and changes to magnesium hydroxide as shown in the following formula (1).

MgO+ H20→Mg(OH)2・・・(1)しかし
て該水酸化マグネシウムは高温仕上焼鈍中に下記(2)
式 %式%(2) で示す熱分解反応を生じ、徐々に水分を放出し、鋼板を
過度に酸化し、磁気的性質を劣化させると共に鋼板の表
面に形成されるグラス皮膜にむらを生じさせる欠点があ
る。
MgO+ H20→Mg(OH)2... (1) Then, the magnesium hydroxide undergoes the following (2) during high-temperature finish annealing.
A thermal decomposition reaction as shown in formula % (2) occurs, gradually releasing moisture, excessively oxidizing the steel plate, deteriorating its magnetic properties, and causing unevenness in the glass film formed on the surface of the steel plate. There are drawbacks.

従来、グラス皮膜の形成方法について種々提案されてい
る。例えば特開昭55−58331号公報では低活性の
MgOを主成分とする焼鈍分離剤を用いることが、特開
昭56−75577号公報ではS。
Conventionally, various methods for forming glass films have been proposed. For example, JP-A No. 55-58331 uses an annealing separator mainly composed of low-activity MgO, and JP-A No. 56-75577 uses S.

S化合物、Sr 、 Sr化合物を添加した焼鈍分離剤
を用いること、特開昭58−9985号公報では非水和
Mgoに硫酸、硫酸塩を添加した焼鈍分離剤を用いるこ
とが提案されている。
It has been proposed to use an annealing separator to which an S compound, Sr, or Sr compound is added. JP-A-58-9985 proposes to use an annealing separator to which sulfuric acid and sulfate are added to non-hydrated Mgo.

(発明が解決しようとする問題点) これらはいづれもそれなシの作用効果があるが、前記水
酸化マグネシウムの分解で生じる欠陥の改善は未だ十分
でなく検討の余地がある。また高温仕上焼鈍においては
該コイルの高温での酸化を防止、あるいは鋼板の不純物
を除去するだめに水素ガスを含む還元ガスが使用されて
いる。この還元ガスは高温仕上焼鈍中にコイルの積層間
に侵入拡散し、脱炭焼鈍時に810□とともに生成した
酸化鉄(ファヤライト)を還元し、グラス皮膜不良の原
因の一つとなる。
(Problems to be Solved by the Invention) All of these have their own effects, but the improvement of the defects caused by the decomposition of magnesium hydroxide is not yet sufficient and there is still room for further investigation. In high-temperature finish annealing, a reducing gas containing hydrogen gas is used to prevent oxidation of the coil at high temperatures or to remove impurities from the steel sheet. This reducing gas penetrates and diffuses between the laminated layers of the coil during high-temperature finishing annealing, reduces iron oxide (fayalite) produced together with 810□ during decarburization annealing, and becomes one of the causes of glass film defects.

本発明者等は高温仕上焼鈍中に水和した水酸化マグネシ
ウムが熱分解し、水分を放出し方向性珪素鋼板を過度に
酸化すること、また還元ガスによシ脱炭焼鈍時に生じた
酸化鉄の還元による等のグラス皮膜不良を同時に解決し
、外観、密着性とも良好なグラス皮膜を形成し、あわせ
て磁気特性も良好な方向性珪素鋼板を製造すべく、実験
し検討を行った。その結果、MgOl主成分とする焼鈍
分離剤中に窒化珪素を添加し、これを、脱炭焼鈍され鋼
板表面に5i02ft含むサブスケールが形成された方
向性珪素鋼板に塗布し、仕上焼鈍すると良好なグラス皮
膜が形成されることを見出した。
The present inventors have discovered that hydrated magnesium hydroxide during high-temperature finish annealing thermally decomposes, releases moisture, and excessively oxidizes grain-oriented silicon steel sheets, and that iron oxide produced during decarburization annealing is caused by reducing gas. Experiments and studies were conducted in order to simultaneously resolve defects in the glass coating caused by reduction of silica, to form a glass coating with good appearance and adhesion, and to produce a grain-oriented silicon steel sheet with good magnetic properties. As a result, silicon nitride was added to an annealing separator mainly composed of MgOl, and this was applied to a grain-oriented silicon steel sheet that had been decarburized and annealed to form subscales containing 5i02ft on the surface of the steel sheet. It was found that a glass film was formed.

(問題点を解決するだめの手段) 本発明はこの知見にもとづいてなされたものであり、以
下に詳細に説明する。
(Means for Solving the Problems) The present invention has been made based on this knowledge, and will be explained in detail below.

本発明の方法は、方向性珪素鋼板のグラス皮膜形成に広
く適用されるものであり、方向性珪素鋼板の鋼成分、お
よび所定板厚に冷間圧延され、次いで脱炭焼鈍されて、
その後焼鈍分離剤が塗布されるまでの製造条件は特定す
る必要はない0例えば出発鋼成分としては仕上焼鈍にて
2次再結晶を発現するだめのインヒビターとしてAtN
 、 MnS 。
The method of the present invention is widely applied to the formation of a glass film on grain-oriented silicon steel sheets, and includes the steel composition of grain-oriented silicon steel sheets, which is cold-rolled to a predetermined thickness, and then decarburized and annealed.
There is no need to specify the manufacturing conditions until the annealing separator is applied.For example, the starting steel component is AtN as an inhibitor to prevent secondary recrystallization from occurring during finish annealing.
, MnS.

Mn5s 、 BN等が生成するように調製され、かつ
必要に応じてCu 、 Sn 、 Cr 、 Ni 、
 Mo 、 Sb 、 P等の元素を含有させる。製造
条件としては例えばスラブを熱間圧延し、焼鈍して1回
または中間焼鈍ftはさんで2回以上の冷間圧延によシ
所定最終板厚とし、脱炭焼鈍する。
It is prepared so that Mn5s, BN, etc. are produced, and Cu, Sn, Cr, Ni,
It contains elements such as Mo, Sb, and P. As for manufacturing conditions, for example, a slab is hot rolled, annealed and cold rolled once or twice or more with intermediate annealing ft to a predetermined final thickness, and then decarburized and annealed.

この脱炭焼鈍により方向性珪素鋼板は脱炭されるととも
に、その鋼板表面には5iO7を含むサブスケール(酸
化層)が形成される。次にMgOを主成分とする焼鈍分
離剤に本発明に従い窒化珪素例えば513N4を添加し
たものを水を懸濁させスラリー状とし、ロールコータ−
等により、鋼板上に塗付jる。焼鈍分離剤中に添加する
窒化珪素は微粒粉状とされ、その添加量は必ずしも特定
する必要はないが、Mg0100重量部に対して2〜1
5重量部が好ましい。
The grain-oriented silicon steel sheet is decarburized by this decarburization annealing, and a subscale (oxide layer) containing 5iO7 is formed on the surface of the steel sheet. Next, according to the present invention, silicon nitride, such as 513N4, is added to an annealing separator mainly composed of MgO, and water is suspended to form a slurry.
etc., to coat the steel plate. The silicon nitride added to the annealing separator is in the form of fine powder, and the amount added does not necessarily have to be specified, but it is 2 to 1 part by weight per 100 parts by weight of Mg0.
5 parts by weight is preferred.

次に乾燥炉にて、鋼板温度を例えば150℃程度まで上
げることによシ、鋼板上のスラリーから水分を除去する
。水分除去後の鋼板上の固形物としては約5〜1497
m2(片面)となる。但し、この温度領域ではMgOの
水和した水酸化マグネシウムの結晶水は除去されない。
Next, water is removed from the slurry on the steel plate by raising the temperature of the steel plate to, for example, about 150° C. in a drying oven. The solid matter on the steel plate after moisture removal is approximately 5 to 1497
m2 (one side). However, in this temperature range, the water of crystallization of magnesium hydroxide in which MgO is hydrated is not removed.

乾燥後の鋼板を直ちにコイル状に巻き取シ、コイル状に
て最終仕上焼鈍を行う。最終仕上焼鈍において鋼板温度
が350〜450℃に達すると前記(2)式にみられる
ように水酸化マグネシウムが熱分解し、水分を放出する
。この熱分解は鋼板温度。
After drying, the steel plate is immediately wound into a coil, and final annealing is performed in the coil. When the steel plate temperature reaches 350 to 450° C. in final finish annealing, magnesium hydroxide is thermally decomposed and releases moisture, as shown in equation (2) above. This thermal decomposition is at the steel plate temperature.

が約500℃程度に達すると完了する。The process is completed when the temperature reaches about 500°C.

一方、513N4は、水分が存在する非酸化性雰囲気中
では200℃の低温でも分解を開始する特性を有するた
めに、前記の水酸化マグネシウムの放出した水分をS 
l 3N4が吸収しく3)の反応が進むと推察される。
On the other hand, 513N4 has the property of starting to decompose even at a low temperature of 200°C in a non-oxidizing atmosphere where moisture is present, so the moisture released by magnesium hydroxide can be removed by S
It is inferred that the reaction 3) proceeds as l3N4 is absorbed.

SiN+6HO→3810  + 4NH,・・・・・
・(3)添加した513N4の作用によシ前記したよう
にMgOの水和した水酸化マグネシウムによる熱分屏に
竿なって放出でれた水分が除去されるために、従来知見
される鋼板のコイル内部で生成した水分が内部よp高温
となったコイルエッソに拡散し、鋼板を著るしく酸化し
、磁気特性を劣化させたシ鋼板表面のグラス皮膜不良を
生じることはない。
SiN+6HO→3810+4NH,・・・・・・
・(3) Due to the action of the added 513N4, as mentioned above, the moisture released as a result of the thermal separation by the hydrated magnesium hydroxide of MgO is removed. Moisture generated inside the coil diffuses into the coil esso, which is heated to a higher temperature than the inside, significantly oxidizes the steel plate, and does not cause defects in the glass coating on the surface of the steel plate, which deteriorates magnetic properties.

又513N4の分屏によシ結果的にはSlO□が鋼板に
外部から補給されるので、鋼板の表面に脱炭焼鈍にて形
成されたSiO2を主成分としたサブスケールを保護し
、 還元雰囲気下での仕上焼鈍過程において該サブスケ
ールが還元されることなく高温迄確保される。これらの
鋼板表面のサブスケールはコイル状での仕上焼鈍過程に
おいて900〜1100℃の鋼板温度で前記の焼鈍分離
剤と反応しフォルステライトラ主成分とするグラス皮膜
を形成する。
In addition, as a result of the 513N4 separation, SlO□ is supplied to the steel plate from the outside, so it protects the subscale mainly composed of SiO2 formed on the surface of the steel plate during decarburization annealing, and creates a reducing atmosphere. In the final annealing process below, the subscale is maintained at high temperatures without being reduced. These subscales on the surface of the steel sheet react with the above-mentioned annealing separator at a steel sheet temperature of 900 to 1100 DEG C. during the final annealing process of the coiled steel sheet to form a glass film containing forsteritetra as a main component.

本発明に従って得られたグラス皮膜は従来法で得られた
ものとは異り、色調は均一で美麗な外観性を呈するのみ
ならず、皮膜密着性ならびに磁気特性にすぐれている。
Unlike those obtained by conventional methods, the glass coating obtained according to the present invention not only has a uniform color tone and a beautiful appearance, but also has excellent coating adhesion and magnetic properties.

(実施例) 次に本発明の実施例について説明する。(Example) Next, examples of the present invention will be described.

Si3.2%、80.02%、 Mn 0.07%、 
A40、028チ、NO,009%を含む珪素鋼スラブ
を3■厚に熱間圧延し、1120℃で3分間の熱延板焼
鈍を施した後、冷間圧延し、最終板厚を0゜3■とした
。次に850℃で3分間露点60℃ H270%からな
るガス雰囲気下で連続焼鈍した後、この方向性珪素鋼板
に、 5113N4をMg0100重量部に対して5重
量部添加した焼鈍分離剤に水を添加して懸濁させスラリ
ー状とし、ロールコータ−で塗付した後、乾燥炉で連続
的に鋼板温度が150℃になる迄昇熱し、水分を除去し
た後、コイル状に巻き取った。次に該コイルを高温仕上
焼鈍炉に装入し、1150℃で焼鈍した。
Si 3.2%, 80.02%, Mn 0.07%,
A silicon steel slab containing A40,028CH, NO,009% was hot rolled to a thickness of 3cm, hot-rolled at 1120°C for 3 minutes, and then cold rolled to a final thickness of 0°. It was set as 3■. Next, after continuous annealing at 850°C for 3 minutes in a gas atmosphere with a dew point of 60°C and 70% H2, water was added to the annealing separator containing 5 parts by weight of 5113N4 per 100 parts by weight of Mg0 to this grain-oriented silicon steel sheet. The slurry was suspended and coated with a roll coater, and then heated in a drying oven until the steel sheet temperature reached 150° C. to remove moisture, and then wound into a coil. Next, the coil was placed in a high-temperature finishing annealing furnace and annealed at 1150°C.

焼鈍後の鋼板の特性を調査し、第1表に示す特性を得た
The properties of the steel plate after annealing were investigated, and the properties shown in Table 1 were obtained.

(発明の効果) 本発明によれば、外観、密着性に優れたグラス皮膜を有
する磁気特性の優れた方向性珪素鋼板を製造することが
できるので産業上極めて有用である。
(Effects of the Invention) According to the present invention, it is possible to produce a grain-oriented silicon steel sheet having a glass film having excellent appearance and adhesion and having excellent magnetic properties, which is extremely useful industrially.

Claims (1)

【特許請求の範囲】[Claims] 方向性珪素鋼を所定板厚に冷間圧延し、次いで脱炭焼鈍
して鋼板表面にSiO_2を含むサブスケールを形成し
、該サブスケール上に酸化マグネシウムを主成分とする
焼鈍分離剤を塗布したのち、仕上焼鈍しグラス皮膜を形
成する方法において、窒化珪素を添加した酸化マグネシ
ウムを主成分とする焼鈍分離剤を用いることを特徴とす
る方向性珪素鋼板のグラス皮膜形成方法。
Grain-oriented silicon steel was cold rolled to a predetermined thickness, then decarburized and annealed to form a subscale containing SiO_2 on the steel plate surface, and an annealing separator containing magnesium oxide as the main component was applied onto the subscale. A method for forming a glass film on a grain-oriented silicon steel sheet, characterized in that, in the method of forming a glass film after finishing annealing, an annealing separator whose main component is magnesium oxide to which silicon nitride is added is used.
JP14380385A 1985-06-29 1985-06-29 Formation of glass film of grain-oriented silicon steel sheet Granted JPS624881A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP14380385A JPS624881A (en) 1985-06-29 1985-06-29 Formation of glass film of grain-oriented silicon steel sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP14380385A JPS624881A (en) 1985-06-29 1985-06-29 Formation of glass film of grain-oriented silicon steel sheet

Publications (2)

Publication Number Publication Date
JPS624881A true JPS624881A (en) 1987-01-10
JPS633025B2 JPS633025B2 (en) 1988-01-21

Family

ID=15347341

Family Applications (1)

Application Number Title Priority Date Filing Date
JP14380385A Granted JPS624881A (en) 1985-06-29 1985-06-29 Formation of glass film of grain-oriented silicon steel sheet

Country Status (1)

Country Link
JP (1) JPS624881A (en)

Also Published As

Publication number Publication date
JPS633025B2 (en) 1988-01-21

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