EP1029113A1 - Method for covering electric steel strips with an annealing separator - Google Patents

Method for covering electric steel strips with an annealing separator

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Publication number
EP1029113A1
EP1029113A1 EP98952601A EP98952601A EP1029113A1 EP 1029113 A1 EP1029113 A1 EP 1029113A1 EP 98952601 A EP98952601 A EP 98952601A EP 98952601 A EP98952601 A EP 98952601A EP 1029113 A1 EP1029113 A1 EP 1029113A1
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EP
European Patent Office
Prior art keywords
annealing separator
chlorine
annealing
steel strips
aqueous solution
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Granted
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EP98952601A
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German (de)
French (fr)
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EP1029113B1 (en
Inventor
Klaus Günther
Heiner Schrapers
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EBG Gesellschaft fuer Elektromagnetische Werkstoffe
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EBG Gesellschaft fuer Elektromagnetische Werkstoffe
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00

Definitions

  • the invention relates to a method for coating electrical steel strips with an oxide powder as an annealing separator by applying an aqueous solution which mainly contains MgO and additionally at least one additive, including a chlorine-containing compound.
  • Electric steel strips are produced in a conventional manner by melting the alloy, pouring off a slab, hot rolling the slab, annealing the hot strip to set the inhibitor phase, cold rolling the hot strip, decarburizing annealing of the cold strip, applying an annealing separator consisting essentially of MgO as adhesive protection in the subsequent Final annealing of the electrical steel strip wound into a coil for secondary recrystallization.
  • Grain-oriented electrical sheets made of silicon steel strips which due to their use in the transformer should have a texture that allows easy magnetization in the rolling direction, the so-called cast texture, are combined with grain growth inhibitors such as AI and N, Mn and S, Cu and S, Mn and Se alloyed.
  • grain growth inhibitors such as AI and N, Mn and S, Cu and S, Mn and Se alloyed.
  • These form compounds, such as A1N, MnS, CuS, MnSe which, finely dispersed, prevent the grains from growing too early during recrystallization annealing. This causes preferential growth of the Goss-oriented grains during the secondary recrystallization.
  • the grain growth-limiting effect of the inhibitors is as finely dispersed a distribution of the particles as possible.
  • the inhibitor distribution can still be influenced until shortly before the onset of selective grain growth. It is certain knowledge that the composition of the glow separator is also of particular importance for the distribution of the grain growth inhibitors. In addition, small amounts of other substances as additives have therefore been added to the annealing separator, which essentially consists of magnesium oxide, in order to achieve an improvement in the surface, an increase in the polarization and a reduction in the magnetic loss.
  • DE 29 47 945 C2 recommends the addition of boron and sodium compounds, EP 0 232 537 B1 the addition of titanium, boron or sulfur compounds.
  • the addition of chlorides was generally considered harmful.
  • the addition of antimony sulfate in combination with Sb, Sr, Ti or Zr chloride is said to bring about improvements in the magnetic properties.
  • antimony sulfate is poorly water-soluble and also toxic.
  • DE 44 09 691 AI a readily water-soluble sodium compound or a finely dispersed oxidic aluminum compound should be added, and a metal chloride can also be added.
  • EP 0 789 093 AI describes halogens or halides as additives.
  • a defined chlorine content in the annealing separator is to be set by adding Mg, Ca, Na and / or K chlorides.
  • a disadvantage of the chlorides listed in these documents is that they are used to introduce elements which, after the long-term annealing, leave disruptive solid residues on the strip surface.
  • the invention is based on the object of avoiding the early degradation of nitridic and / or sulfidic inhibitors during the heating-up phase for the final annealing or to simulate nitridic inhibitors in this phase.
  • the inhibitors in this phase are influenced primarily by reactions of the annealing gas with the base material or the inhibitors contained in it.
  • the composition of the glow separator plays an important role.
  • ammonium chloride (NHC1 or NH 4 Cl 'nH 2 O) is added to the aqueous solution as an additive.
  • the amount of additive is chosen so that the chlorine concentration, based on the mass fraction MgO in the annealing separator, is 0.01 to 0.10 mass%, preferably 0.02 to 0.05 mass%.
  • sodium pyrophosphate can be added as a further additive, preferably in an amount such that the sodium concentration, based on the proportion of MgO in the annealing separator, is adjusted to 0.02 to 0.05 mass%.
  • the concentrations of chlorine and sodium in the annealing separator are set independently of one another by the process according to the invention. Chlorine and sodium are introduced into the aqueous solution in the form of various compounds, so that an independent optimization of the respective concentration of chlorine or sodium is ensured.
  • a particular advantage of adding chlorine and possibly sodium to the annealing separator in the case of highly permeable electrical sheet according to the invention is that the magnetic properties react significantly less strongly to differences in the conditions during the final annealing. Since the final annealing is carried out in the coil, it is inevitable that differences in the annealing conditions in Band cross and longitudinal direction occur. The differences in the annealing conditions mainly concern the dew point of the annealing gas.
  • the magnesium oxide applied in the form of an aqueous slurry and then dried inevitably contains a proportion of magnesium hydroxide. This magnesium hydroxide is thermally decomposed into magnesium oxide and water during the final annealing heating phase. The water released increases the dew point of the hot gas. An unfavorable dew point can adversely affect the inhibitor distribution.
  • ammonium chloride as a chlorine dispenser for the glow separator is of particular importance and has two decisive advantages over other known chlorine compounds.
  • the binding partner of the chlorine should be removed in an environmentally friendly manner under the thermal conditions of the final annealing via the gas phase, without leaving any solid residues.
  • Ammonium chloride fulfills both conditions excellently.
  • the NH 3 group is thermally split off. This gas also increases the nitrogen partial pressure between the coil turns as a prerequisite for avoiding degradation of nitridic inhibitors in the steel strip and is further broken down into harmless N 2 and H.
  • sodium pyrophosphate as an additional additive to the annealing separator, a further improvement in the magnetic properties can be achieved.
  • Sodium pyrophosphate supports the property-improving effect of the addition of chlorine. It also counteracts a clear embroidery of the steel band.
  • Fig. 1 shows the results based on the magnetic loss P ⁇ 7th
  • the adjustment of the chlorine concentration by ammonium chloride according to the invention leads to a significant improvement in the magnetic properties compared to the use of antimony chloride.
  • Example 2
  • the chlorine and sodium concentrations in the annealing separator were set to the following values using the additions of ammonium chloride and sodium pyrophosphate:
  • Table 3 shows the results based on the magnetic loss P ⁇ / 7 .
  • the magnetic properties are significantly improved.
  • the loss of magnetization increases by approx. 7% off.
  • the effectiveness of a laser treatment performed on the finished belt for the domain refinement is with the Na and Cl concentrations in the annealing separator set according to the invention are particularly large.
  • Table 5 shows the results based on the magnetic loss P ⁇ , 7th
  • the magnetic loss is reduced by approximately 2%.
  • An additional adjustment of the sodium concentration according to the invention lowers the loss again by 3%.
  • the effectiveness of laser treatment is significantly increased, as shown in FIG. 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Cell Separators (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to a process for the coating of electric steel strips with an oxide powder as annealing separator by the application of an aqueous solution which contains mainly MgO and also at least one additive, including a chlorine-containing compound. The characterizing feature of the invention is that the additive added to the aqueous solution is ammonium chloride (NH4Cl or NH4Cl.nH2O).

Description

Verfahren zum Beschichten von Elektrostahlbändern mit einem GlühseparatorProcess for coating electrical steel strips with an annealing separator
Die Erfindung betrifft ein Verfahren zum Beschichten von Elektrostahlbändern mit einem Oxidpulver als Glühseparator durch Auftragen einer wäßrigen Lösung, die hauptsächlich MgO und zusätzlich mindestens ein Additiv, darunter eine chlorhaltige Verbindung, enthält.The invention relates to a method for coating electrical steel strips with an oxide powder as an annealing separator by applying an aqueous solution which mainly contains MgO and additionally at least one additive, including a chlorine-containing compound.
Die Erzeugung von Elektrostahlbändern erfolgt in herkömmlicher Weise durch Schmelzen der Legierung, Abgießen einer Bramme, Warmwalzen der Bramme, Glühen des Warmbandes zur Einstellung der Inhibitorphase, Kaltwalzen des Warmbandes, Entkohlungsglühen des Kaltbandes, Auftragen eines im wesentlichen aus MgO bestehenden Glühseparators als Klebschutz bei der anschließenden Schlußglühung des zu einem Coil gewickelten Elektrostahlbandes zur Sekundärrekristallisation.Electric steel strips are produced in a conventional manner by melting the alloy, pouring off a slab, hot rolling the slab, annealing the hot strip to set the inhibitor phase, cold rolling the hot strip, decarburizing annealing of the cold strip, applying an annealing separator consisting essentially of MgO as adhesive protection in the subsequent Final annealing of the electrical steel strip wound into a coil for secondary recrystallization.
Kornorientierte Elektrobleche aus Siliziumstahlbändern, die aufgrund ihres Einsatzes im Transformator eine Textur aufweisen sollen, die eine leichte Magnetisierbarkeit in Walzrichtung erlaubt, die sog. Gosstextur, werden mit Kornwachstums-Inhibitoren, wie AI und N, Mn und S, Cu und S, Mn und Se legiert. Diese bilden Verbindungen, wie A1N, MnS, CuS, MnSe, die, feindispers ausgeschieden, bei den Rekristallisationsglühungen ein zu frühes Wachstum der Körner verhindern. Dadurch wird während der Sekundärrekristallisation ein bevorzugtes Wachstum der Goss-orientierten Körner hervorgerufen. Von Bedeutung für die kornwachstumsbegrenzende Wirkung der Inhibitoren ist eine möglichst gleichmäßige feindisperse Verteilung der Partikel. Dies geschieht während der Warmbandglühung und/oder während eines nach der Entkohlung durchzuführenden AufStickprozesses . Bis kurz vor dem Einsetzen des selektiven Kornwachstums läßt sich die Inhibitorverteilung noch beeinflussen. Dabei ist gesicherter Wissensstand, daß der Zusammensetzung des Glühseparators eine besondere Bedeutung auch für die Verteilung der Kornwachstums-Inhibitoren zukommt. Man hat dem im wesentlichen aus Magnesiumoxid bestehenden Glühseparator daher in jeweils geringen Mengen andere Stoffe als Additive zugesetzt, um eine Verbesserung der Oberfläche, eine Erhöhung der Polarisation und eine Verringerung des Ummagnetisierungsverlustes zu erreichen.Grain-oriented electrical sheets made of silicon steel strips, which due to their use in the transformer should have a texture that allows easy magnetization in the rolling direction, the so-called cast texture, are combined with grain growth inhibitors such as AI and N, Mn and S, Cu and S, Mn and Se alloyed. These form compounds, such as A1N, MnS, CuS, MnSe, which, finely dispersed, prevent the grains from growing too early during recrystallization annealing. This causes preferential growth of the Goss-oriented grains during the secondary recrystallization. Of importance for the grain growth-limiting effect of the inhibitors is as finely dispersed a distribution of the particles as possible. This takes place during hot strip annealing and / or during an embroidering process to be carried out after decarburization. The inhibitor distribution can still be influenced until shortly before the onset of selective grain growth. It is certain knowledge that the composition of the glow separator is also of particular importance for the distribution of the grain growth inhibitors. In addition, small amounts of other substances as additives have therefore been added to the annealing separator, which essentially consists of magnesium oxide, in order to achieve an improvement in the surface, an increase in the polarization and a reduction in the magnetic loss.
Die DE 29 47 945 C2 empfiehlt den Zusatz von Bor- und Natriumverbindungen, die EP 0 232 537 Bl den Zusatz von Titan-, Bor- oder Schwefelverbindungen. Zunächst hielt man den Zusatz von Chloriden generell für schädlich. Gemäß der DE 34 40 344 soll jedoch die Zugabe von Antimonsulfat in Kombination mit Sb-, Sr-, Ti- oder Zr- Chlorid Verbesserungen der magnetischen Eigenschaften bewirken. Antimonsulfat ist jedoch schlecht wasserlöslich und zudem toxisch. Entsprechend der Lehre nach DE 44 09 691 AI sollen eine gut wasserlösliche Natriumverbindung oder eine feindisperse oxidische Aluminiumverbindung zugegeben werden, wobei auch noch zusätzlich ein Metallchlorid hinzugegeben werden kann. EP 0 789 093 AI beschreibt Halogene oder Halogenide als Additive. Nach EP 0 416 420 A2 soll ein definierter Chlorgehalt im Glühseparator durch die Zugabe von Mg-, Ca-, Na- und/oder K-Chloriden eingestellt werden. Nachteilig an den in diesen Schriften aufgeführten Chloriden ist, daß mit ihnen Elemente eingebracht werden, die nach der Langzeitglühung störende Feststoffrückstände auf der Bandoberfläche hinterlassen.DE 29 47 945 C2 recommends the addition of boron and sodium compounds, EP 0 232 537 B1 the addition of titanium, boron or sulfur compounds. At first, the addition of chlorides was generally considered harmful. According to DE 34 40 344, however, the addition of antimony sulfate in combination with Sb, Sr, Ti or Zr chloride is said to bring about improvements in the magnetic properties. However, antimony sulfate is poorly water-soluble and also toxic. According to the teaching according to DE 44 09 691 AI, a readily water-soluble sodium compound or a finely dispersed oxidic aluminum compound should be added, and a metal chloride can also be added. EP 0 789 093 AI describes halogens or halides as additives. According to EP 0 416 420 A2, a defined chlorine content in the annealing separator is to be set by adding Mg, Ca, Na and / or K chlorides. A disadvantage of the chlorides listed in these documents is that they are used to introduce elements which, after the long-term annealing, leave disruptive solid residues on the strip surface.
Der Erfindung liegt nun die Aufgabe zugrunde, einen frühzeitigen Abbau von nitridischen und/oder sulfidischen Inhibitoren während der Aufheizphase zur Schlußglühung zu vermeiden oder nitridische Inhibitoren in dieser Phase nachzubilden. Die Beeinflussung der Inhibitoren in dieser Phase läuft maßgeblich über Reaktionen des Glühgases mit dem Grundwerkstoff bzw. den in ihm enthaltenen Inhibitoren ab. Die Zusammensetzung des Glühseparators spielt dabei eine wesentliche Rolle.The invention is based on the object of avoiding the early degradation of nitridic and / or sulfidic inhibitors during the heating-up phase for the final annealing or to simulate nitridic inhibitors in this phase. The inhibitors in this phase are influenced primarily by reactions of the annealing gas with the base material or the inhibitors contained in it. The composition of the glow separator plays an important role.
Zur Lösung der gestellten Aufgabe wird bei dem gattungsgemäßen Verfahren erfindungsgemäß vorgeschlagen, daß der wäßrigen Lösung als Additiv Ammoniumchlorid (NHC1 bzw. NH4CI ' nH20) zugesetzt wird. Die Menge an Additiv wird dabei so gewählt, daß die Chlorkonzentration, bezogen auf den Masseanteil MgO im Glühseparator, 0,01 bis 0,10 Masse-%, bevorzugt 0,02 bis 0,05 Masse-%, beträgt .To achieve the object, it is proposed according to the invention in the generic method that ammonium chloride (NHC1 or NH 4 Cl 'nH 2 O) is added to the aqueous solution as an additive. The amount of additive is chosen so that the chlorine concentration, based on the mass fraction MgO in the annealing separator, is 0.01 to 0.10 mass%, preferably 0.02 to 0.05 mass%.
Als weiteres Additiv kann erfindungsgemäß Natriumpyrophosphat, bevorzugt in einer solchen Menge zugesetzt werden, daß die Natrium-Konzentration, bezogen auf den Anteil von MgO im Glühseparator, auf 0,02 bis 0,05 Masse-% eingestellt wird. Durch die erfindungsgemäß dem Glühseparator zugesetzten Additive wird die Schichtbildung so gesteuert, daß der Glasfilm bei niedrigen Temperaturen gebildet wird und eine so hohe Dichtigkeit aufweist, daß eine Wechselwirkung zwischen den Glühgasen und den Inhibitoren im Elektrostahlband verhindert wird.According to the invention, sodium pyrophosphate can be added as a further additive, preferably in an amount such that the sodium concentration, based on the proportion of MgO in the annealing separator, is adjusted to 0.02 to 0.05 mass%. By means of the additives added to the annealing separator according to the invention, the layer formation is controlled in such a way that the glass film is formed at low temperatures and has such a high level of tightness that an interaction between the annealing gases and the inhibitors in the electrical steel strip is prevented.
Bei Durchführung des erfindungsgemäßen Verfahrens wird neben einer Verbesserung des Ummagnetisierungsverlustes eine deutliche Erhöhung der Orientierungsschärfe, d.h. eine ausgeprägte Gosstextur und dadurch großes Verbesserungspotential durch eine am Fertigband durchzuführende Domänenfeinung, z.B. durch Laserbehandlung, erreicht. Darüberhinaus ergeben sich Vorteile bezüglich leichter Verfügbarkeit der vorgesehen Additive, ihre gute Wasserlöslichkeit, kostengünstige und einfache Durchführbarkeit sowie toxikologische und ökologische Verträglichkeit.When carrying out the method according to the invention, in addition to an improvement in the magnetic loss, a significant increase in the sharpness of orientation, i.e. a distinctive cast texture and thus great potential for improvement through a domain refinement to be carried out on the finished belt, e.g. achieved by laser treatment. In addition, there are advantages with regard to the easy availability of the additives provided, their good water solubility, inexpensive and easy to carry out, and toxicological and ecological compatibility.
Die Einstellung der Konzentrationen von Chlor und Natrium im Glühseparator erfolgt nach dem erfindungsgemäßen Verfahren unabhängig voneinander. Chlor und Natrium werden in Form verschiedener Verbindungen in die wäßrige Lösung eingebracht, so daß eine unabhängige Optimierung der jeweiligen Konzentration an Chlor bzw. Natrium gewährleistet ist.The concentrations of chlorine and sodium in the annealing separator are set independently of one another by the process according to the invention. Chlorine and sodium are introduced into the aqueous solution in the form of various compounds, so that an independent optimization of the respective concentration of chlorine or sodium is ensured.
Ein besonderer Vorteil bei der erfindungsgemäßen Zugabe von Chlor und ggf. Natrium zum Glühseparator bei hochpermeablem Elektroblech ist, daß die magnetischen Eigenschaften deutlich weniger stark auf Unterschiede der Bedingungen beim Schlußglühen reagieren. Da das Schlußglühen im Coil durchgeführt wird, ist es unvermeidbar, daß Unterschiede in den Glühbedingungen in Bandquer- und längsrichtung auftreten. Die Unterschiede bei den Glühbedingungen betreffen vor allem den Taupunkt des Glühgases. Das in der Form einer wäßrigen Aufschlämmung aufgetragene und anschließend getrocknete Magnesiumoxid beinhaltet zwangsläufig einen Anteil an Magnesiumhydroxid. Dieses Magnesiumhydroxid wird während der Aufheizphase der Schlußglühung thermisch in Magnesiumoxid und Wasser zersetzt. Das freiwerdende Wasser erhöht den Taupunkt des Glühgases. Ein ungünstiger Taupunkt kann zu einer nachteiligen Beeinträchtigung der Inhibitorverteilung führen.A particular advantage of adding chlorine and possibly sodium to the annealing separator in the case of highly permeable electrical sheet according to the invention is that the magnetic properties react significantly less strongly to differences in the conditions during the final annealing. Since the final annealing is carried out in the coil, it is inevitable that differences in the annealing conditions in Band cross and longitudinal direction occur. The differences in the annealing conditions mainly concern the dew point of the annealing gas. The magnesium oxide applied in the form of an aqueous slurry and then dried inevitably contains a proportion of magnesium hydroxide. This magnesium hydroxide is thermally decomposed into magnesium oxide and water during the final annealing heating phase. The water released increases the dew point of the hot gas. An unfavorable dew point can adversely affect the inhibitor distribution.
Die Wahl von Ammoniumchlorid als Chlorspender für den Glühseparator hat besondere Bedeutung und zwei entscheidende Vorteile gegenüber anderen bekannten Chlorverbindungen. Zum einen soll der Bindungspartner des Chlors unter den thermischen Bedingungen der Schlußglühung über die Gasphase umweltverträglich abtransportiert werden, ohne Feststoffrückstände zu hinterlassen. Ferner soll, wie vorerwähnt, der frühe Abbau nitridischer Inhibitoren im Elektrostahlband verhindert werden. Beide Bedingungen erfüllt Ammoniumchlorid in hervorragender Weise. Bei der Schlußglühung erfolgt die thermische Abspaltung der NH3-Gruppe . Dieses Gas erhöht darüberhinaus den Stickstoffpartialdruck zwischen den Coilwindungen als Voraussetzung für die Vermeidung eines Abbaus nitridischer Inhibitoren im Stahlband und wird im weiteren in unschädliches N2 und H zersetzt. Durch Einsatz von Natriumpyrophosphat als zusätzliches Additiv zum Glühseparator kann eine weitere Verbesserung der magnetischen Eigenschaften erreicht werden. Natriumpyrophosphat unterstützt die eigenschafts- verbessernde Wirkung des Chlorzusatzes. Außerdem wirkt es einer deutlichen Aufstickung des Stahlbandes entgegen.The choice of ammonium chloride as a chlorine dispenser for the glow separator is of particular importance and has two decisive advantages over other known chlorine compounds. On the one hand, the binding partner of the chlorine should be removed in an environmentally friendly manner under the thermal conditions of the final annealing via the gas phase, without leaving any solid residues. Furthermore, as mentioned above, the early breakdown of nitride inhibitors in the electrical steel strip is to be prevented. Ammonium chloride fulfills both conditions excellently. During the final annealing, the NH 3 group is thermally split off. This gas also increases the nitrogen partial pressure between the coil turns as a prerequisite for avoiding degradation of nitridic inhibitors in the steel strip and is further broken down into harmless N 2 and H. By using sodium pyrophosphate as an additional additive to the annealing separator, a further improvement in the magnetic properties can be achieved. Sodium pyrophosphate supports the property-improving effect of the addition of chlorine. It also counteracts a clear embroidery of the steel band.
Anhand der folgenden Beispiele wird die Erfindung näher erläutert.The invention is illustrated by the following examples.
Beispiel 1example 1
Bei der betrieblichen Fertigung von hochpermeablen kornorientierten Elektroblechen der Dicke 0,23 mm wurden die Chlorkonzentrationen durch Ammoniumchlorid und zum Vergleich durch Antimonchlorid als Additive zum Glühseparator eingestellt.In the operational production of highly permeable grain-oriented electrical sheets with a thickness of 0.23 mm, the chlorine concentrations were adjusted using ammonium chloride and, for comparison, using antimony chloride as additives to the annealing separator.
Tabelle 1 Chlorkonzentration in ppm, bezogen auf MgO im GlühseparatorTable 1 Chlorine concentration in ppm, based on MgO in the annealing separator
Fig. 1 zeigt die Ergebnisse anhand des Ummagnetisierungsverlustes Pι7. Die erfindungsgemäße Einstellung der Chlorkonzentration durch Ammoniumchlorid führt im Vergleich zu der Anwendung von Antimonchlorid zu einer deutlichen Verbesserung der magnetischen Eigenschaften . Beispiel 2Fig. 1 shows the results based on the magnetic loss Pι 7th The adjustment of the chlorine concentration by ammonium chloride according to the invention leads to a significant improvement in the magnetic properties compared to the use of antimony chloride. Example 2
Bei der betrieblichen Fertigung von hochpermeablen kornorientierten Elektroblechen der Dicke 0,30 mm wurden die Chlor- und Natriumkonzentrationen im Glühseparator durch die Zusätze Ammoniumchlorid und Natriumpyrophosphat auf folgende Werte eingestellt :In the operational production of highly permeable grain-oriented electrical sheets with a thickness of 0.30 mm, the chlorine and sodium concentrations in the annealing separator were set to the following values using the additions of ammonium chloride and sodium pyrophosphate:
Tabelle 2 Cl- und Na-Konzentrationen in ppmTable 2 Cl and Na concentrations in ppm
Tabelle 3 zeigt die Ergebnisse anhand des Ummagnetisierungsverlustes Pι/7.Table 3 shows the results based on the magnetic loss Pι / 7 .
Tabelle 3 Ummagnetisierungsverlust P, 7 in W/kgTable 3 Magnetic loss P, 7 in W / kg
Durch die erfindungsgemäße Einstellung der Natrium- und Chlorkonzentrationen werden die magnetischen Eigenschaften deutlich verbessert. Der Ummagnetisierungsverlust nimmt um ca . 7 % ab. Die Effektivität einer am Fertigband durchgeführten Laserbehandlung zur Domänenfeinung ist bei den mit erfindungsgemäß eingestellten Na- und Cl-Konzentrationen im Glühseparator besonders groß.By adjusting the sodium and chlorine concentrations according to the invention, the magnetic properties are significantly improved. The loss of magnetization increases by approx. 7% off. The effectiveness of a laser treatment performed on the finished belt for the domain refinement is with the Na and Cl concentrations in the annealing separator set according to the invention are particularly large.
Beispiel 3Example 3
Bei der betrieblichen Fertigung von hochpermeablen kornorientierten Elektroblechen der Dicke 0,27 mm wurden die Chlor- und Natriumkonzentrationen im Glühseparator nacheinander durch die Zusätze Ammoniumchlorid und Natriumpyrophosphat auf folgende Werte eingestellt:In the operational production of highly permeable grain-oriented electrical sheets with a thickness of 0.27 mm, the chlorine and sodium concentrations in the annealing separator were successively adjusted to the following values by adding ammonium chloride and sodium pyrophosphate:
Tabelle 4Table 4
Cl- und Na-Konzentrationen in ppmCl and Na concentrations in ppm
Tabelle 5 zeigt die Ergebnisse anhand des Ummagnetisierungsverlustes Pι,7.Table 5 shows the results based on the magnetic loss Pι, 7th
Tabelle 5Table 5
Ummagnetisierungsverlust Pj 7 in W/kgMagnetic loss Pj 7 in W / kg
Durch die erfindungsgemäße Einstellung der Chlorkonzeήtrationen wird der Ummagnetisierungsverlust um ca. 2 % gesenkt. Eine erfindungsgemäß zusätzliche Einstellung der Natriumkonzentration senkt den Verlust nochmals um 3 % . Die Effektivität einer Laserbehandlung wird deutlich gesteigert, wie Fig 2 ausweist. By adjusting the chlorine concentrations according to the invention, the magnetic loss is reduced by approximately 2%. An additional adjustment of the sodium concentration according to the invention lowers the loss again by 3%. The effectiveness of laser treatment is significantly increased, as shown in FIG. 2.

Claims

Patentansprüσhe Patent claims
1. Verfahren zum Beschichten von Elektrostahlbändern mit einem Glühseparator durch Auftragen einer wäßrigen Lösung, die hauptsächlich MgO und zusätzlich mindestens ein Additiv, darunter eine chlorhaltige Verbindung, enthält, d a d u r c h g e k e n n z e i c h n e t , daß der wäßrigen Lösung als Additiv Ammoniumchlorid (NH4C1 bzw. NH4CI ' nH20) zugesetzt wird.1. A method for coating electrical steel strips with an annealing separator by applying an aqueous solution which mainly contains MgO and additionally at least one additive, including a chlorine-containing compound, characterized in that the aqueous solution as an additive ammonium chloride (NH 4 C1 or NH 4 CI 'nH 2 0) is added.
2. Verfahren nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , daß der wäßrigen Lösung soviel Ammoniumchlorid zugesetzt wird, daß die Chlorkonzentration 0,01 bis 0,10 Masse-%, bezogen auf den Masseanteil MgO, im Glühseparator ist.2. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that so much ammonium chloride is added that the chlorine concentration is 0.01 to 0.10 mass%, based on the mass fraction MgO, in the annealing separator.
3. Verfahren nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t , daß die Chlorkonzentration auf 0,02 bis 0,05 Masse-%, bezogen auf den Masseanteil MgO im Glühseparator, eingestellt wird.3. The method of claim 2, d a d u r c h g e k e n n z e i c h n e t that the chlorine concentration to 0.02 to 0.05 mass%, based on the mass fraction MgO in the annealing separator, is set.
4. Verfahren nach einem der Ansprüche 1 bis 3, d a d u r c h g e k e n n z e i c h n e t , daß der wäßrigen Lösung als weiteres Additiv Natriumpyrophosphat (Na4P20 bzw. Na4P207 • n H20) zugesetzt wird.4. The method according to any one of claims 1 to 3, characterized in that the aqueous solution as a further additive sodium pyrophosphate (Na 4 P 2 0 or Na 4 P 2 0 7 • n H 2 0) is added.
5. Verfahren nach Anspruch 4, d a d u r c h g e k e n n z e i c h n e t , daß die Natriumkonzentration auf 0,02 bis 0,05 Masse-%, • bezogen auf den Anteil von MgO im Gühseparator, eingestellt wird. 5. The method of claim 4, d a d u r c h g e k e n n z e i c h n e t that the sodium concentration to 0.02 to 0.05 mass%, • based on the proportion of MgO in the Gühseparator, is set.
EP98952601A 1997-11-12 1998-09-18 Method for covering electric steel strips with an annealing separator Expired - Lifetime EP1029113B1 (en)

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DE19750066A DE19750066C1 (en) 1997-11-12 1997-11-12 Process for coating electrical steel strips with an annealing separator
DE19750066 1997-11-12
PCT/EP1998/005960 WO1999024639A1 (en) 1997-11-12 1998-09-18 Method for covering electric steel strips with an annealing separator

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CN102443736B (en) * 2010-09-30 2013-09-04 宝山钢铁股份有限公司 Method for producing high magnetic flux-density oriented silicon steel product
KR101480498B1 (en) * 2012-12-28 2015-01-08 주식회사 포스코 Oriented electrical steel sheet and method for manufacturing the same
US11827961B2 (en) 2020-12-18 2023-11-28 Vacuumschmelze Gmbh & Co. Kg FeCoV alloy and method for producing a strip from an FeCoV alloy

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