JP2690841B2 - Annealing Separator for grain oriented electrical steel sheet for obtaining uniform high-strength glass coating and excellent magnetic properties - Google Patents
Annealing Separator for grain oriented electrical steel sheet for obtaining uniform high-strength glass coating and excellent magnetic propertiesInfo
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- JP2690841B2 JP2690841B2 JP4249818A JP24981892A JP2690841B2 JP 2690841 B2 JP2690841 B2 JP 2690841B2 JP 4249818 A JP4249818 A JP 4249818A JP 24981892 A JP24981892 A JP 24981892A JP 2690841 B2 JP2690841 B2 JP 2690841B2
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- oriented electrical
- magnetic properties
- electrical steel
- steel sheet
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Description
【０００１】[0001]
【産業上の利用分野】本発明は方向性電磁鋼板の製造に
際し、最終仕上焼鈍工程において、均一で高張力のグラ
ス被膜を形成すると共に優れた磁気特性の得られる方向
性電磁鋼板の焼鈍分離剤に関する。FIELD OF THE INVENTION The present invention relates to an annealing separator for grain-oriented electrical steel sheets which can form a uniform and high-strength glass coating in the final finishing annealing step in the production of grain-oriented electrical steel sheets and can obtain excellent magnetic properties. Regarding
【０００２】[0002]
【従来の技術】通常、方向性電磁鋼板は、Ｓｉ２．５〜
４０％含有する素材スラブを熱延し、焼鈍と１回又は中
間焼鈍をはさむ２回以上の冷延により最終板厚とされ
る。次いで連続焼鈍炉においてＮ2 ＋Ｈ2 又はＨ2 雰囲
気中でＰ H2 O ／Ｐ H2 をコントロールして脱炭焼鈍を
行い、脱炭処理を行うと同時にＳｉＯ2 を主体とする酸
化膜層を形成する。2. Description of the Related Art Usually, grain-oriented electrical steel sheets have Si2.5-
The raw material slab containing 40% is hot-rolled and annealed and cold-rolled once or twice or more with intermediate annealing to obtain the final plate thickness. Then N 2 + with H 2 or H 2 atmosphere to control the P H 2 O / P H 2 perform decarburization annealing in a continuous annealing furnace, the oxide film layer to simultaneously mainly SiO 2 Doing decarburization Form.
【０００３】その後、ＭｇＯを主成分とする焼鈍分離剤
をスラリー状としてコーティングロール等により鋼板表
面に塗布し、コイルに巻取り最終仕上焼鈍を行い、二次
再結晶、純化反応、グラス被膜形成を行い、通常は絶縁
被膜剤処理とヒートフラットニングを行って最終製品と
される。Thereafter, an annealing separator containing MgO as a main component is applied as a slurry to the surface of the steel sheet by a coating roll or the like, wound on a coil and subjected to final finishing annealing to carry out secondary recrystallization, purification reaction and glass film formation. Then, it is usually treated with an insulating coating agent and heat flattened to obtain the final product.
【０００４】この方向性電磁鋼板は〈００１〉軸をもつ
（１１０）〈００１〉結晶が高温の二次再結晶で優先的
に成長する現象を利用している。この二次再結晶過程で
低表面エネルギーをもつ（１１０）面結晶が優先的に成
長し、鋼中にインヒビターとして微細に分散しているＡ
ｌＮ，ＭｎＳ等によりその成長を抑えられている他の結
晶を侵蝕するものに（１１０）〈００１〉結晶が優先的
に成長するものと考えられている。This grain-oriented electrical steel sheet utilizes a phenomenon in which a (110) <001> crystal having a <001> axis grows preferentially by high temperature secondary recrystallization. During this secondary recrystallization process, (110) face crystals with low surface energy grow preferentially and are finely dispersed as an inhibitor in the steel A
It is considered that the (110) <001> crystal grows preferentially to the one that corrodes other crystals whose growth is suppressed by 1N, MnS and the like.
【０００５】従って優れた方向性電磁鋼板を製造するた
めには、鋼中インヒビターＡｌＮ，ＭｎＳ等の分散状態
とこれらの分解までの制御が重要である。最終仕上焼鈍
におけるインヒビターの変化は脱炭焼鈍で形成した鋼板
表面の酸化膜、焼鈍分離剤及び最終仕上焼鈍での熱サイ
クルや雰囲気条件等により影響を受ける。Therefore, in order to produce an excellent grain-oriented electrical steel sheet, it is important to control the dispersion state of the inhibitors AlN, MnS, etc. in the steel and their decomposition. The change of the inhibitor in the final finish annealing is affected by the oxide film on the surface of the steel sheet formed by the decarburization annealing, the annealing separator, the thermal cycle in the final finishing annealing, the atmospheric conditions and the like.
【０００６】これらの中でとりわけ焼鈍分離剤としてグ
ラス被膜形成剤としてのＭｇＯの影響力は大きい。これ
はＭｇＯ粒子の純度、物性値等が最終焼鈍での昇温過程
における脱炭時に形成した酸化膜の変化やグラス被膜の
形成時期、形成速度、コイル板間の雰囲気の酸化度等に
多大な影響をもたらして、これによりインヒビターの安
定性に影響を与えるからである。Among these, MgO as a glass film forming agent has a great influence as an annealing separator. This is because the purity and physical properties of the MgO particles are greatly affected by changes in the oxide film formed during decarburization in the temperature rising process during final annealing, the timing of formation of the glass film, the formation rate, the degree of oxidation of the atmosphere between the coil plates, etc. This has the effect of affecting the stability of the inhibitor.
【０００７】焼鈍分離剤ＭｇＯは脱炭焼鈍で形成された
ＳｉＯ2 主体の酸化膜と反応して通常グラス被膜と呼ぶ
フォルステライト被膜を形成する（２ＭｇＯ＋ＳｉＯ2
→Ｍｇ2 ＳｉＯ4 ）。又この際、鋼インヒビターともに
ＡｌＮを用いる場合同時に脱インヒビターに伴って生じ
るＡｌ2 Ｏ3 と、ＭｇＯ，ＳｉＯ2 等とによるスピネル
構造をもつ化合物が、フォルステライトの直下に形成す
る。The annealing separator MgO reacts with the SiO 2 -based oxide film formed by decarburization annealing to form a forsterite film usually called a glass film (2MgO + SiO 2
→ Mg 2 SiO 4 ). Further, at this time, when AlN is used as the steel inhibitor, a compound having a spinel structure of Al 2 O 3 and MgO, SiO 2 or the like, which is simultaneously formed with the deinhibitor, is formed directly under the forsterite.
【０００８】このグラス被膜形成においては、ＭｇＯと
ＳｉＯ2 の反応は純粋系においては１６００℃近い高温
でなければ反応が生じず、酸化膜の性状、仕上焼鈍条件
の制御と共に焼鈍分離剤の性状として、不純物、粒径、
粒子形状、表面状態、活性度等を制御して仕上焼鈍サイ
クルの中でいかに低温から、均一なフォルステライト形
成反応を行わせるかが良好なグラス被膜と優れた磁気特
性を得るための重要なカギとなる。In the formation of this glass film, the reaction between MgO and SiO 2 does not occur in a pure system unless the temperature is close to 1600 ° C. Therefore, the properties of the oxide film and the finish annealing conditions are controlled, and the properties of the annealing separator are determined. , Impurities, particle size,
An important key to obtaining a good glass coating and excellent magnetic properties is to control the particle shape, surface condition, activity, etc., so that a uniform forsterite formation reaction can be performed from a low temperature in the finishing annealing cycle. Becomes
【０００９】このように方向性電磁鋼板の商品価値を決
定する上で重要な磁気特性とグラス被膜形成にＭｇＯの
品質の影響が大きいことから、ＭｇＯ品質の改善は方向
性電磁鋼板の製造技術にとって重要な課題となってい
る。Since the quality of MgO has a great influence on the magnetic properties and the glass film formation which are important in determining the commercial value of grain-oriented electrical steel sheet, improvement of the quality of MgO is important for the production technology of grain-oriented electrical steel sheet. It has become an important issue.
【００１０】ＭｇＯの性状の中でグラス被膜形成とこれ
に関連してインヒビターの安定性に影響する因子として
は、ＭｇＯの活性度（反応性）、粒度、純度、鋼板への
密着性等があり、鋼板に塗布される際には、水和の進行
度合、粒子の分散状態、塗布量等がある。このため、良
質の方向性電磁鋼板を得るためには、これらの条件を最
適化することが重要である。Among the properties of MgO, factors that influence the formation of the glass film and the stability of the inhibitor related thereto include the activity (reactivity) of MgO, the particle size, the purity, and the adhesion to the steel sheet. When applied to a steel sheet, there are a degree of progress of hydration, a dispersed state of particles, an applied amount, and the like. Therefore, in order to obtain a good quality grain-oriented electrical steel sheet, it is important to optimize these conditions.
【００１１】通常ＭｇＯは、水に懸濁させてスラリー状
として鋼板に塗布し乾燥される。この際、ＭｇＯの製造
条件によっては例えば高活性の場合、水とのスラリー調
整段階でＭｇＯ→Ｍｇ（ＯＨ）2 となる水和反応が生
じ、コイル内に水分を持込む結果、板間露点を高め、且
つ不均一にする。Usually, MgO is suspended in water, applied as a slurry to a steel sheet and dried. At this time, depending on the production conditions of MgO, for example, in the case of high activity, a hydration reaction of MgO → Mg (OH) 2 occurs in the slurry preparation step with water, and as a result of bringing moisture into the coil, the dew point between the plates becomes Increase and make uneven.
【００１２】このため、仕上焼鈍昇温過程で過剰な追加
酸化が生じ、スケール、ガスマーク、ピンホール、変色
等の重度の被膜欠陥を引きおこす。ところが、一般的に
はこの高水和ＭｇＯにおける問題点を解決するために採
用される方法は、高温焼成による方法である。この方法
としては、例えば特開昭５５−７３８２３号公報に開示
されている方法がある。For this reason, excessive additional oxidation occurs in the course of the temperature increase during finish annealing, causing serious film defects such as scales, gas marks, pinholes, and discoloration. However, a method generally adopted to solve the problem in this highly hydrated MgO is a method by high temperature firing. As this method, for example, there is a method disclosed in JP-A-55-73823.
【００１３】このような焼成温度を上げることが得られ
た低活性ＭｇＯでは水和性の低下は得られるが、反応性
や付着性が低下する欠点がある。又、特開昭６２−１５
６２２６号公報にはＭｇＯ粒子の最表面を活性化する方
法が提案されている。この方法では高温焼成してＭｇＯ
の最表面層のみに気相中で水和層を形成するものでこれ
により、グラス被膜を磁気特性のかなりの向上が得られ
ている。The low activity MgO obtained by increasing the firing temperature as described above can reduce the hydration property, but has a drawback that the reactivity and the adhesive property are reduced. Also, JP-A-62-15
Japanese Patent No. 6226 proposes a method of activating the outermost surface of MgO particles. In this method, high temperature firing is carried out to obtain MgO.
A hydrated layer is formed only in the outermost surface layer in the gas phase, and this has significantly improved the magnetic properties of the glass coating.
【００１４】更に特公平４−２５３４９号公報にはＭｇ
Ｏ中の不純物の調整に着目するものとしてＣａ化合物と
Ｂ化合物の複合添加によるものがある。これによりＭｇ
Ｏの付着力が顕著に改善し、グラス被膜形成反応性も向
上して、グラス被膜、磁気特性の優れた方向性電磁鋼板
が得られるものである。Further, in Japanese Patent Publication No. 4-25349, Mg is disclosed.
One that focuses on the adjustment of impurities in O is by the combined addition of a Ca compound and a B compound. This makes Mg
The adhesive force of O is remarkably improved and the reactivity of forming a glass film is also improved, and a glass film and a grain-oriented electrical steel sheet having excellent magnetic properties can be obtained.
【００１５】このようにＭｇＯ条件を改善することによ
り、反応性が改善されかなりの改善効果が得られてい
る。しかし、鋼成分脱炭焼鈍、仕上焼鈍によっては被膜
特性、磁気特性が不安定になる場合があり、未だ完全な
る技術とは言えず、更なる改善が望まれている。By improving the MgO conditions in this way, the reactivity is improved and a considerable improvement effect is obtained. However, the film properties and magnetic properties may become unstable depending on the decarburization annealing and finishing annealing of the steel components, and it cannot be said that this is a perfect technology, and further improvement is desired.
【００１６】[0016]
【発明が解決しようとする課題】従来のＭｇＯにおける
フォルステライト被膜の反応向上技術は、焼成温度低下
による高活性化や低活性ＭｇＯを用い、スラリー調整時
の強制水和或いは焼成後の低活性ＭｇＯの粒子表面処理
によるものである。The conventional technique for improving the reaction of the forsterite coating on MgO uses high activation or low activity MgO by lowering the firing temperature, and uses forced hydration during slurry preparation or low activity MgO after firing. This is due to the surface treatment of particles.
【００１７】これらの技術では前者では高活性における
水和水分による板間の過酸化の問題があり、これを防止
するため後者の技術においてもＭｇＯ長期保存時の変
質、表面水和層の変化、撹拌等のスラリー調整条件によ
る変動、塗布乾燥時の乾燥条件等の変動による影響はさ
けられない。In the former technique, there is a problem of interoxidation between plates due to hydrated water in the high activity in the former technique, and in order to prevent this problem, the latter technique also deteriorates MgO during long-term storage, changes in surface hydration layer, Fluctuations due to slurry adjustment conditions such as stirring and fluctuations in drying conditions during coating and drying are inevitable.
【００１８】即ち、これらはいずれもＭｇＯの表層に付
着反応させるＨ2 Ｏによるグラス被膜形成反応の促進効
果を利用したものであり、Ｈ2 Ｏをメインに利用しない
フォルステライト被膜の低温形成技術が確立されなけれ
ば、これらの問題は解決されない。That is, all of them utilize the accelerating effect of the glass film forming reaction by H 2 O which causes the adhesion reaction to the surface layer of MgO, and a low temperature forming technique of a forsterite film which does not mainly use H 2 O is used. If not established, these problems will not be resolved.
【００１９】本発明においては、この対策として低水和
ＭｇＯの反応性向上策として、ＭｇＯの純度、物性値や
その製造技術等について膨大なラボテストと現場実験に
よる検討を行った。In the present invention, as a measure for improving the reactivity of low hydrated MgO, a vast amount of laboratory tests and field experiments were conducted on the purity and physical properties of MgO and the manufacturing technique thereof as a measure for improving this.
【００２０】[0020]
【課題を解決するための手段】本発明は、焼鈍分離剤と
して使用するＭｇＯの前記問題点の解決策として、水酸
化マグネシウム、炭酸マグネシウム、塩基性炭酸マグネ
シウム、硫酸マグネシウム、塩化マグネシウム、高純度
酸化マグネシウムを原料として高反応性ＭｇＯを製造す
る際の、製造工程における原料調整段階において、Ｍ
ｇ，Ｃａ，Ｂａ，Ｃｕ，Ｆｅ，Ｚｎ，Ｍｎ，Ｚｒ，Ｃ
ｏ，Ｎｉ，Ａｌ，Ｓｎ，Ｖの中から選ばれる塩素化合物
の１種又は２種以上を、Ｃｌとして０．００５〜０．０
６０％含有するように調整すること、及び〔Ｃｌ
（％）〕×〔Ｂ（％）〕＝０．００１〜０．００４にな
るようにＢを含有すること、更に測定温度３０℃におけ
るＣＡＡ値５０〜１５０秒で、粒子径１０μｍ以下のも
のが７０％以上であること、にある。 以上の構成とする
ことにより、低水和でありながら、下地酸化膜との反応
によりフォルステライトの形成性が著しく優れることを
見出した。As a solution to the above problems of MgO used as an annealing separator, the present invention provides magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, magnesium sulfate, magnesium chloride, high-purity oxidation. When producing highly reactive MgO using magnesium as a raw material , M
g, Ca, Ba, Cu, Fe, Zn, Mn, Zr, C
One or two or more chlorine compounds selected from o, Ni, Al, Sn, and V is used as Cl and is 0.005 to 0.0
Adjust to contain 60%, and [Cl
(%)] × [B (%)] = 0.001 to 0.004
So that it contains B, and at a measurement temperature of 30 ° C
That in CAA value of 50 to 150 seconds, even the particle size not greater than 10μm
Is 70% or more . It has been found that, with the above-mentioned structure, the forsterite forming property is remarkably excellent due to the reaction with the underlying oxide film even though the hydration is low.
【００２１】これにより、従来技術では実現できなかっ
たＭｇＯ表面の水和層による反応性向上効果なしでも、
グラスフィルムが均一で、磁気特性がコイル全面、全長
にわたって良好な方向性電磁鋼板を得ることに成功し
た。As a result, even without the effect of improving the reactivity due to the hydrated layer on the surface of MgO, which could not be realized by the prior art,
We succeeded in obtaining a grain-oriented electrical steel sheet with a uniform glass film and good magnetic properties over the entire surface and entire length of the coil.
【００２２】本発明の出発材としては鋼成分としてＳｉ
２．５〜４．０％を含む珪素鋼スラブを公知の方法で熱
延し、１回又は焼鈍をはさむ２回以上の冷延を行い、最
終板厚とし、次いで脱炭焼鈍を行って、鋼板表面にＳｉ
Ｏ2 を主体とする酸化膜を形成したいわゆる脱炭焼鈍板
が用いられる。この鋼板上に焼鈍分離剤として前記塩素
化合物と硼素化合物を微量に調整してＭｇＯを水スラリ
ーとして均一に分散し、連続ラインにおいてコーティン
グロール等で塗布し、２５０〜３５０℃の温度で乾燥し
コイルに巻取られる。The starting material of the present invention is Si as a steel component.
A silicon steel slab containing 2.5 to 4.0% is hot-rolled by a known method, cold-rolled once or twice with annealing, to obtain a final plate thickness, and then decarburized-annealed. Si on steel plate surface
A so-called decarburized annealed plate having an oxide film mainly composed of O 2 is used. A small amount of the chlorine compound and the boron compound as annealing separators was prepared on this steel sheet to uniformly disperse MgO as a water slurry, which was applied in a continuous line by a coating roll or the like and dried at a temperature of 250 to 350 ° C. to form a coil. To be wound up.
【００２３】この際、焼鈍分離剤ＭｇＯ中にはグラス被
膜形成の反応補助剤、板間露点調整剤、インヒビター補
助剤として酸化物、硼酸塩、硫酸塩、硫化物等が、鋼成
分の特にインヒビターに応じて添加配合される。At this time, in the annealing separator MgO, a reaction auxiliary agent for forming a glass film, a dew point adjusting agent between plates, and an inhibitor auxiliary agent such as oxide, borate, sulfate, sulfide, etc., are particularly inhibitors of steel components. It is added and blended according to.
【００２４】このように処理されたコイルは、最終仕上
焼鈍としてバッチ式、或いは連続式炉内で、１２００℃
×２０hrのような高温、長時間の処理がなされ、グラス
フィルム形成、二次再結晶純化反応が同時に行われる。The coil thus treated is subjected to final finishing annealing at 1200 ° C. in a batch type or continuous type furnace.
The glass film formation and the secondary recrystallization purification reaction are carried out at the same time by treatment at a high temperature of × 20 hr for a long time.
【００２５】方向性電磁鋼板においては、この際のグラ
ス被膜の形成時期、形成速度、形成量、形成状態等がイ
ンヒビターＡｌＮ，ＭｎＳ等の分解速度に影響を与えた
り、グラス被膜の張力、純化反応等に影響を及ぼす結
果、グラス被膜と磁気特性を左右するものである。焼鈍
分離剤ＭｇＯは、このグラス被膜形成に対して最も大き
い役割をもつため、その物性値のコントロールは重要で
ある。In the grain-oriented electrical steel sheet, the formation timing, formation rate, formation amount, formation state, etc. of the glass coating at this time influence the decomposition rate of the inhibitors AlN, MnS, etc., the tension of the glass coating, the purification reaction. As a result, it influences the glass coating and magnetic properties. Since the annealing separating agent MgO has the largest role in forming this glass film, it is important to control its physical property values.
【００２６】このようにして処理されたグラス被膜形成
後のコイルは、連続ラインにおいて余剰の焼鈍分離剤を
水洗等により除去と軽酸洗の後、絶縁被膜剤を塗布し、
その焼付と形状矯正、歪取焼鈍をかねてヒートフラット
ニングが行われる。The coil thus treated with the glass film is removed from the excess annealing separator in a continuous line by washing with water and light pickling, and then an insulating coating agent is applied.
Heat flattening is performed while also performing the baking, the shape correction, and the strain relief annealing.
【００２７】この際方向性電磁鋼板はとりわけ高磁束密
度材においては被膜張力による鉄損、磁歪等の改善効果
が大きいことから、仕上焼鈍で形成したグラス被膜の張
力効果を更に補強するため、絶縁被膜剤成分としても張
力付与型のものが用いられる。At this time, since the grain-oriented electrical steel sheet has a great effect of improving iron loss, magnetostriction and the like due to coating tension, especially in a high magnetic flux density material, in order to further reinforce the tension effect of the glass coating formed by finish annealing, insulation A tension imparting type is also used as the coating agent component.
【００２８】この張力付与型の絶縁被膜剤成分として
は、コロイダル物質としてＳｉＯ2 ，ＺｒＯ2 ，ＳｎＯ
2 等を固形分として１００重量部に対し、Ａｌ，Ｍｇ，
Ｃａ等の第１リン酸塩の１種又は２種以上を１３０〜２
００重量部、クロム酸、クロム酸塩の１種又は２種以上
をＣｒＯ3 として１２〜４０重量部配合したものを用い
るが、経済的に高張力被膜が得られるため好適である。As the components of this tension imparting type insulating coating agent, SiO 2 , ZrO 2 and SnO as colloidal substances are used.
100 parts by weight of 2 etc. as solid content, Al, Mg,
130 to 2 of 1 type or 2 types or more of primary phosphates, such as Ca.
It is preferable to use 12 parts by weight to 40 parts by weight of CrO 3 containing one part or two or more kinds of chromic acid and chromate, in an amount of 12 to 40 parts by weight, because a high-strength coating is economically obtained.
【００２９】この後、鉄損を更に改善しようとする場合
には、レーザー、歯形ロール、エッチング、高部メッキ
等により、圧延方向とほぼ直角方向に線状、点状に間隔
と深さをコントロールして、歪、疵、メッキ層等を処理
して磁区細分化処理が行われる。After that, when the iron loss is to be further improved, the intervals and depths are controlled linearly or in a dot-like manner by a laser, a tooth profile roll, etching, high part plating or the like. Then, distortion, flaws, plating layers, etc. are processed to perform magnetic domain subdivision processing.
【００３０】次に本発明における構成技術の限定理由に
ついて述べる。まず、本発明に適用されるＭｇＯの成分
としてはＣｌ化合物をＭｇ，Ｃａ，Ｂａ，Ｃｕ，Ｆｅ，
Ｚｎ，Ｍｎ，Ｔｉ，Ｚｒ，Ｃｏ，Ｎｉ，Ａｌ，Ｓｎ等の
中から選ばれる１種又は２種以上をＣｌとして０．００
５〜０．０６％含有する。Next, the reasons for limitation of the construction technique in the present invention will be described. First, as a component of MgO applied to the present invention, a Cl compound is used as Mg, Ca, Ba, Cu, Fe,
One or two or more selected from Zn, Mn, Ti, Zr, Co, Ni, Al, Sn and the like is set as Cl and is 0.00
5 to 0.06% is contained.
【００３１】これらのＣｌ化合物は低活性の本質的には
反応性の低い粒子の融点を適正に低下させ、従来技術の
ように粒子表面のＨ2 Ｏや他の酸化物等の助けなしにグ
ラス被膜を低温で形成する。These Cl compounds properly lower the melting point of low activity, essentially non-reactive particles and, as in the prior art, without the aid of H 2 O and other oxides on the surface of the particles, glass. The coating is formed at low temperature.
【００３２】Ｃｌ化合物がＣｌとして０．００５％未満
ではこのような効果が弱く、グラス被膜が均一に形成で
きない。又、これにより仕上焼鈍昇温過程での雰囲気ガ
スのシール性が弱いため、良好な二次再結晶が生じず、
磁束密度や、鉄損特性が劣化する。If the Cl compound is less than 0.005% as Cl, such an effect is weak and a glass film cannot be formed uniformly. Further, due to this, the sealing property of the atmospheric gas in the temperature process of finish annealing is weak, so that good secondary recrystallization does not occur,
Magnetic flux density and iron loss characteristics deteriorate.
【００３３】一方、Ｃｌ化合物が０．０６％超では、グ
ラス被膜形成時の被膜層の融点が下がりすぎる結果、過
酸化現象特有のピンホール状の欠陥が生じたり、過剰の
Ｃｌ化合物の高温分解時に生じるＣｌによって、酸化
膜、グラス被膜が腐蝕されて、最終的なグラス被膜の厚
みを薄くしたり、不均一なガスマーク状のムラを生じ
る。０．００５〜０．０６％の範囲ではこれらの問題が
なく均一な高張力グラス被膜を形成し、磁気特性が著し
く改善される。On the other hand, the ultra-Cl compound 0.06%, a result of the melting point of the coating layer during the glass film formation is too low, or cause peroxidation phenomenon defects inherent pinhole-shaped, high-temperature decomposition of excess Cl compound The oxide film and the glass film are corroded by Cl generated at times, and the thickness of the final glass film is thinned or nonuniform gas mark-like unevenness occurs. Within the range of 0.005 to 0.06%, a uniform high-strength glass film is formed without these problems, and the magnetic properties are remarkably improved.
【００３４】次にこのＣｌの含有量に応じてＭｇＯ中の
Ｂ量は規制される。即ち〔Ｃｌ（％）〕×〔Ｂ（％）〕
＝０．００１〜０．００４になるようにＢを含有するこ
とが望ましい。Next, the amount of B in MgO is regulated according to the content of Cl. That is, [Cl (%)] × [B (%)]
B should be contained so that
And is desirable.
【００３５】これはＭｇＯ中のＢ含有量によって上記Ｃ
ｌによる効果が影響を受けるからであり、Ｃｌ量が０．
００５〜０．０６％の範囲では上式の範囲内に制御され
ることが望ましい。This depends on the content of B in MgO.
This is because the effect of Cl is affected, and the Cl amount is 0.
In the range of 005 to 0.06%, it is desirable to control within the range of the above formula.
【００３６】Ｂ量がこの範囲から外れるとグラス被膜形
成効果が弱まったり、過酸化現象が生じる場合がある。
特にＢ量が上式の範囲を超える場合に影響が顕著で、こ
の場合はグラス被膜層の融点が下がりすぎる結果、良質
のグラス被膜層が形成できず、後の高温Ｈ2 焼鈍時に還
元されて、薄く、不均一な被膜層となる。If the amount of B deviates from this range, the effect of forming a glass film may be weakened or a peroxide phenomenon may occur.
In particular, when the amount of B exceeds the range of the above formula, the effect is remarkable, and in this case, the melting point of the glass coating layer is too low, so that a good quality glass coating layer cannot be formed and is reduced during the subsequent high temperature H 2 annealing. A thin, non-uniform coating layer results.
【００３７】これらのＣｌ化合物、Ｂ化合物はＭｇＯ製
造工程原料調整〜最終粉砕工程のどこで添加しても良い
が、望ましくは原料調整の段階に添加するのが良い。こ
れは添加する化合物がベースＭｇＯ中に含有され、使用
段階で均一な表面反応をもたらすからである。These Cl compound and B compound may be added anywhere in the raw material adjustment process to the final pulverization process of the MgO manufacturing process, but it is preferable to add them in the stage of raw material adjustment. This is because the compound to be added is contained in the base MgO and brings about a uniform surface reaction at the use stage.
【００３８】又、本発明におけるＭｇＯのＣＡＡ値は液
温３０℃の測定値で５０〜１５０秒である。これは、本
発明のＭｇＯの反応性が主にＣｌ量とこれにバランスす
るＢ量によって保たれているためこのような不活性タイ
プのＭｇＯの方がむしろ良好なグラス被膜と磁気特性を
得るのに好適である。The CAA value of MgO in the present invention is 50 to 150 seconds when measured at a liquid temperature of 30 ° C. This is because the reactivity of MgO of the present invention is maintained mainly by the amount of Cl and the amount of B which balances with the amount of Cl, and thus such an inactive type MgO can obtain better glass coating and magnetic properties. Suitable for
【００３９】このため、ＣＡＡ値が５０秒未満の高活性
域ではスラリー調整時の水和水分の持込みにより、鋼板
間が過酸化となってインヒビターの減少を過度に早めた
り、グラス被膜が厚くなりすぎたり、不均一なるためグ
ラス被膜特性、磁気特性が劣化する。Therefore, in the high activity region where the CAA value is less than 50 seconds, the hydrated water content is brought in during the slurry preparation, so that the space between the steel sheets becomes peroxidized and the inhibitor decreases excessively quickly, or the glass coating becomes thick. The glass coating properties and magnetic properties are deteriorated due to excessive or non-uniformity.
【００４０】一方ＣＡＡ値が１５０秒超では、本発明の
ような成分のＭｇＯにおいてもＭｇＯ粒子自体の不活性
をカバーできず、薄く不均一なグラス被膜となる。この
ため密着性が劣化したり、グラス被膜の張力の低下によ
って良好な鉄損値が得られない。[0040] In contrast CAA value of 150 sec ultra can not cover the inert MgO particles themselves in components of MgO as in the present invention, a thin nonuniform glass film. As a result, the adhesion is deteriorated and the tensile strength of the glass coating is lowered, so that a good iron loss value cannot be obtained.
【００４１】又、ＭｇＯの粒子径としては本発明におい
ては１０μｍ以下の粒子が７０％以上である。ＭｇＯの
粒子径は下地のＳｉＯ2 主体の酸化膜との反応における
フォルステライト形成における反応性確保において重要
である。In the present invention, the particle diameter of MgO is 10% or less and 70% or more. The particle size of MgO is important for ensuring reactivity in forsterite formation in the reaction with the underlying SiO 2 -based oxide film.
【００４２】即ち、粒子径が粗大粒子であると鋼板への
良好な密着性が得られない。このため本発明のＣｌ，Ｂ
量やＭｇＯの水和水分等の相乗効果でＭｇＯ粒子の表面
を軟化、溶融させ、下地ＳｉＯ2 層に拡散反応を行わせ
るフォルステライト形成反応に不利になるからである。
１０μｍ以下７０％以上では、本発明のＭｇＯ成分で
は、良好なフォルステライト形成が得られる。That is, if the particle size is coarse, good adhesion to the steel sheet cannot be obtained. Therefore, Cl, B of the present invention
This is because the synergistic effect of the amount and the hydrated water content of MgO softens and melts the surface of the MgO particles, which is disadvantageous to the forsterite formation reaction that causes the underlying SiO 2 layer to undergo a diffusion reaction.
When the thickness is 10 μm or less and 70% or more, good forsterite formation is obtained with the MgO component of the present invention.
【００４３】[0043]
実施例１ 重量％でＣ：０．０７５、Ｓｉ：３．２５、Ｍｎ：０．
０６３、Ｓ：０．０２４、Ａｌ：０．０３１、Ｎ：０．
００７８残部不可避の不純物とＦｅよりなる高磁束密度
方向性電磁鋼板素材を公知の方法で熱延、焼鈍、冷延を
行い、最終板厚０．２２５mmとした。Example 1 C: 0.075, Si: 3.25, Mn: 0.
063, S: 0.024, Al: 0.031, N: 0.
A high magnetic flux density grain-oriented electrical steel sheet material consisting of Fe and the unavoidable impurities in the balance was hot-rolled, annealed and cold-rolled by known methods to give a final sheet thickness of 0.225 mm.
【００４４】この後Ｎ2 ２５％＋Ｈ2 ７５％の湿潤雰囲
気中で脱炭焼鈍した後、表１に示す組成を有するＭｇＯ
を鋼板に塗布し、乾燥し、コイルとして巻取り１２００
℃×２０hrの最終仕上焼鈍を行った。Then, after decarburization annealing in a humid atmosphere of N 2 25% + H 2 75%, MgO having the composition shown in Table 1 was used.
Is applied to a steel plate, dried, and wound as a coil 1200
Final finishing annealing was performed at ℃ × 20hr.
【００４５】この後、絶縁被膜剤として３０％コロイド
状シリカ７０ml、５０％第１リン酸マグネシウム５０m
l、クロム酸５ｇからなる溶液を塗布し、焼付とヒート
フラットニング処理を行い最終成品とした。この試験に
おけるグラス被膜形成状況、磁気特性を表２に示す。Thereafter, 70 ml of 30% colloidal silica and 50 m of 50% monobasic magnesium phosphate as an insulating coating agent.
A solution consisting of 1 g of chromic acid and 5 g of chromic acid was applied, followed by baking and heat flattening treatment to obtain a final product. Table 2 shows the glass film formation state and magnetic properties in this test.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【表２】 [Table 2]
【００４８】この結果、塩化物の種類をとわず、塩素量
として０．００２％と低いものはいずれもグラス被膜形
成状況が不良で密着性、被膜張力が悪く、磁気特性も不
良であった。一方、塩素量が０．０７０％と高いケース
では、いずれもガスマーク状のムラが多く、グラス被膜
も薄くなり、密着性、被膜張力、磁気特性も同様にして
不良であった。しかし、塩素量０．０１〜０．０５％で
はグラス被膜は厚く、均一に形成され、密着性、被膜張
力が良好で、磁気特性も良好であった。 実施例２ 重量％でＣ：０．０７８、Ｓｉ：３．１５、Ｍｎ：０．
０６５、Ｓ：０．０２４、Ａｌ：０．０２７、Ｎ：０．
００７９残部不可避の不純物とＦｅよりなる高磁束密度
方向性電磁鋼板素材を実施例１と同様にして熱延、焼
鈍、冷延を行い、最終板厚０．２９mmとした。As a result, regardless of the type of chloride, the chlorine content as low as 0.002% was inferior in the glass film formation state, the adhesion and film tension were poor, and the magnetic properties were also poor. . On the other hand, in the case where the chlorine content was as high as 0.070%, there were many gas mark-like irregularities, the glass coating became thin, and the adhesiveness, coating tension, and magnetic properties were similarly poor. However, when the chlorine content was 0.01 to 0.05%, the glass coating was thick and formed uniformly, the adhesion and coating tension were good, and the magnetic properties were also good. Example 2 C: 0.078, Si: 3.15, Mn: 0.
065, S: 0.024, Al: 0.027, N: 0.
A high magnetic flux density grain-oriented electrical steel sheet material composed of Fe and the unavoidable balance was hot-rolled, annealed and cold-rolled in the same manner as in Example 1 to give a final sheet thickness of 0.29 mm.
【００４９】この後Ｎ2 ２５％＋Ｈ2 ７５％の湿潤雰囲
気中で脱炭焼鈍した後、表３に示す組成を有するＭｇＯ
を鋼板に塗布し、乾燥し、コイルとして巻取り１２００
℃×２０hrの最終仕上焼鈍を行った。Thereafter, after decarburization annealing in a humid atmosphere of N 2 25% + H 2 75%, MgO having the composition shown in Table 3 was obtained.
Is applied to a steel plate, dried, and wound as a coil 1200
Final finishing annealing was performed at ℃ × 20hr.
【００５０】この後絶縁被膜剤を実施例１と同様にして
処理し、最終成品とした。この試験におけるグラス被膜
形成状況、磁気特性を表４に示す。Thereafter, the insulating coating agent was treated in the same manner as in Example 1 to obtain the final product. Table 4 shows the glass coating formation state and magnetic properties in this test.
【００５１】[0051]
【表３】 [Table 3]
【００５２】[0052]
【表４】 [Table 4]
【００５３】この結果、塩化物添加により調整したＭｇ
Ｏでは塩素０．００２０％のものはＢ量によらず、グラ
ス被膜、磁気特性とも不良であった。塩素として０．０
２００〜０．０６００％添加したものは、ＭｇＯ中のＢ
量との関係でグラス被膜と磁気特性の両立する領域があ
り、〔Ｃｌ量（％）〕×〔Ｂ量（％）〕で０．００１〜
０．００４％の範囲内で何れも良好な特性が得られた。As a result, Mg adjusted by adding chloride
In the case of O, chlorine having a content of 0.0020% had poor glass coating and magnetic properties regardless of the amount of B. 0.0 as chlorine
200 to 0.0600% is added to B in MgO.
There is an area where the glass coating and magnetic properties are compatible with each other in relation to the amount, and [Cl amount (%)] × [B amount (%)] is 0.001 to
Within the range of 0.004%, good characteristics were obtained.
【００５４】一方この領域を外れたものは、グラス被膜
が不均一であったり、磁気特性も本発明域に比較してや
や劣る結果となった。On the other hand, those outside this region resulted in non-uniform glass coating and magnetic properties slightly inferior to those of the present invention.
【００５５】[0055]
【発明の効果】本発明はＭｇＯの製造過程で塩素化合物
をＣｌとして０．００５〜０．０６０％含有するように
調整し、且つ同時に含有するＢ量との間に〔Ｃｌ
（％）〕×〔Ｂ（％）〕＝０．００１〜０．００４とな
るように成分を調整すること、更にＭｇＯのＣＡＡ値と
粒子径を特定域に制御することによりグラス被膜が均一
で、磁気特性が著しく改善されて焼鈍分離剤とそれによ
る方向性電磁鋼板の製造方法を提供しうる。INDUSTRIAL APPLICABILITY According to the present invention, a chlorine compound is adjusted to be contained in an amount of 0.005 to 0.060% as Cl in the process of producing MgO, and at the same time, the amount of B is contained between [Cl]
(%)] × [B (%)] = 0.001 to 0.004, and by controlling the CAA value and particle diameter of MgO within a specific range, the glass coating is made uniform. Thus, the magnetic properties are remarkably improved, and an annealing separator and a method for producing a grain-oriented electrical steel sheet using the same can be provided.
【図１】本発明のＭｇＯの成分領域を示す図である。斜
線領域が本発明におけるグラス被膜と磁気特性の両立が
得られる領域である。FIG. 1 is a diagram showing a component region of MgO of the present invention. The shaded area is an area where compatibility between the glass coating and magnetic properties of the present invention is obtained.
Claims (1)
ム、塩基性炭酸マグネシウム、硫酸マグネシウム、塩化
マグネシウム、高純度酸化マグネシウムをマグネシウム
化合物原料として高反応性の方向性電磁鋼板用焼鈍分離
剤を製造する際の、製造工程における原料調整段階にお
いて、Ｍｇ，Ｃａ，Ｂａ，Ｃｕ，Ｆｅ，Ｚｎ，Ｍｎ，Ｚ
ｒ，Ｃｏ，Ｎｉ，Ａｌ，Ｓｎ，Ｖの中から選ばれる塩素
化合物の１種又は２種以上を、Ｃｌとして０．００５〜
０．０６０％、およびＢを〔Ｃｌ（％）〕×〔Ｂ
（％）〕＝０．００１〜０．００４となるように、それ
ぞれ含有するよう調整され、且つ、測定温度３０℃にお
けるＣＡＡ値５０〜１５０秒で、粒子径１０μｍ以下の
ものが７０％以上であることを特徴とする、均一な高張
力グラス被膜と優れた磁気特性を得るための方向性電磁
鋼板用焼鈍分離剤。1. Annealing separation for highly reactive grain-oriented electrical steel sheets using magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, magnesium sulfate, magnesium chloride, and high-purity magnesium oxide as raw materials for magnesium compounds.
In the production of agents, and have your <br/> the material preparation step in the production process, Mg, Ca, Ba, Cu , Fe, Zn, Mn, Z
One or two or more kinds of chlorine compounds selected from r, Co, Ni, Al, Sn, and V are used as Cl and 0.005 to
0.060% , and B in [Cl (%)] × [B
(%)] = 0.001 to 0.004
A uniform high-strength glass coating, characterized by containing 70% or more of particles each having a CAA value of 50 to 150 seconds at a measurement temperature of 30 ° C. and a particle diameter of 10 μm or less, which is adjusted to contain each of them. An annealing separator for grain-oriented electrical steel sheets to obtain magnetic properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4249818A JP2690841B2 (en) | 1992-09-18 | 1992-09-18 | Annealing Separator for grain oriented electrical steel sheet for obtaining uniform high-strength glass coating and excellent magnetic properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4249818A JP2690841B2 (en) | 1992-09-18 | 1992-09-18 | Annealing Separator for grain oriented electrical steel sheet for obtaining uniform high-strength glass coating and excellent magnetic properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06101059A JPH06101059A (en) | 1994-04-12 |
| JP2690841B2 true JP2690841B2 (en) | 1997-12-17 |
Family
ID=17198651
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4249818A Expired - Fee Related JP2690841B2 (en) | 1992-09-18 | 1992-09-18 | Annealing Separator for grain oriented electrical steel sheet for obtaining uniform high-strength glass coating and excellent magnetic properties |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017169853A1 (en) | 2016-03-30 | 2017-10-05 | タテホ化学工業株式会社 | Magnesium oxide for annealing separator, and grain-oriented electromagnetic steel sheet |
| US11001907B2 (en) | 2016-03-30 | 2021-05-11 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet |
| US11566297B2 (en) | 2016-03-30 | 2023-01-31 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet |
| US11591232B2 (en) | 2016-03-30 | 2023-02-28 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5696404B2 (en) * | 2010-09-06 | 2015-04-08 | Ｊｆｅスチール株式会社 | Method for producing grain-oriented electrical steel sheet |
| JP7181441B1 (en) * | 2021-03-31 | 2022-11-30 | タテホ化学工業株式会社 | Magnesium oxide for annealing separator and grain-oriented electrical steel sheet |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01177376A (en) * | 1988-01-08 | 1989-07-13 | Nippon Steel Corp | Annealing separating agent for grain-oriented magnetic steel sheet for obtaining uniform glass coating film and excellent magnetic characteristic |
| EP0416420B1 (en) * | 1989-09-08 | 1994-12-14 | Armco Inc. | Magnesium oxide coating for electrical steels and the method of coating |
-
1992
- 1992-09-18 JP JP4249818A patent/JP2690841B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017169853A1 (en) | 2016-03-30 | 2017-10-05 | タテホ化学工業株式会社 | Magnesium oxide for annealing separator, and grain-oriented electromagnetic steel sheet |
| CN109072329A (en) * | 2016-03-30 | 2018-12-21 | 达泰豪化学工业株式会社 | Annealing separation agent magnesia and orientation electrical sheet |
| US11001907B2 (en) | 2016-03-30 | 2021-05-11 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet |
| US11097955B2 (en) | 2016-03-30 | 2021-08-24 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separator, and grain-oriented electromagnetic steel sheet |
| US11566297B2 (en) | 2016-03-30 | 2023-01-31 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet |
| US11591232B2 (en) | 2016-03-30 | 2023-02-28 | Tateho Chemical Industries Co., Ltd. | Magnesium oxide for annealing separators, and grain-oriented magnetic steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06101059A (en) | 1994-04-12 |
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