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WO1999053107A1 - Procede permettant de produire un film d'isolation en forsterite sur la surface de toles d'acier a grains orientes et electrotechniquement anisotropes - Google Patents

Procede permettant de produire un film d'isolation en forsterite sur la surface de toles d'acier a grains orientes et electrotechniquement anisotropes Download PDF

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Publication number
WO1999053107A1
WO1999053107A1 PCT/EP1999/002394 EP9902394W WO9953107A1 WO 1999053107 A1 WO1999053107 A1 WO 1999053107A1 EP 9902394 W EP9902394 W EP 9902394W WO 9953107 A1 WO9953107 A1 WO 9953107A1
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WO
WIPO (PCT)
Prior art keywords
steel sheet
mgo
annealing
temperature
hydrogen
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.)
Ceased
Application number
PCT/EP1999/002394
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German (de)
English (en)
Inventor
Georg Königbauer
Zirlin Mikhail Borisovich
Nosov Alksey Dmitrievich
Nosov Sergey Konstantinovich
Lobanov Mikhail Lvovich
Kavtrev Vladislav Mikhailovich
Kavtrev Aleksey Vladislavovich
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Individual
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Application filed by Individual filed Critical Individual
Publication of WO1999053107A1 publication Critical patent/WO1999053107A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with 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
    • 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
    • C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
    • C21D8/1272—Final recrystallisation annealing
    • 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
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere

Definitions

  • the present invention relates to the field of iron metallurgy or black metallurgy, and in particular to a method for producing a forsterite insulation film on a surface of grain-oriented anisotropic electrotechnical steel sheets with a small thickness of typically 0.2 to 0.4 mm, as used in the production of magnetic lines from transformers.
  • a finished electrotechnical steel sheet should have a high magnetic flux density or induction and low power losses in order to agnetization. Furthermore, they should have a permanent surface insulation, which is usually created by applying a ceramic layer to the surface, namely as a thin insulation film with good adhesion to the metal surface.
  • the desired magnetic properties are achieved by the formation of a perfect fin texture in the steel (110) [001] in the course of the second or secondary recrystallization.
  • This perfect rib texture is formed when the normal grain growth in the final heat treatment is slowed down by adding an inhibitor phase.
  • the steel manufacturing processes are based on sulfide, nitride and others. Differentiated processing methods.
  • Decarburization / temper annealing is usually carried out in the production of steel with sulfide inhibition at temperatures of 800 to 900 ° C. in a moist mixture of hydrogen and nitrogen.
  • the carbon is burned or excreted, and a Fayalith film made of Si0 2 -FeO forms on the surface.
  • the sheet is then coated with a MgO-containing water slurry with a low degree of hydration and wound into a spool or a rolled-up tape.
  • the subsequent high-temperature annealing with a slow heating to usually 1150 to 1280 ° C is said to develop the secondary recrystallization for selective growth of the crystal grains with the (110) [001] orientation and a thin, uniform forsterite film made of MgO-SiO 2 on the surface form good adhesion to the metal, which forms the base layer for maintaining high-quality electrical surface insulation.
  • high temperature annealing involves slow heating or holding within a temperature range of 850 ° to 1000 ° C in an atmosphere of dry hydrogen to obtain a perfect cubic edge orientation (rib texture) in the process of secondary recrystallization as the end result of high temperature annealing.
  • a separator containing MgO is applied to the steel sheet, and the sheet treated in this way is wound into a coil and the wound sheet is annealed, the temperature being kept constant at 800-920 ° C. for at least 10 hours, so that it is completely secondary Develop recrystallized grains with a (110) [001] orientation.
  • a final annealing takes place at a temperature in the range of 1000 - 1200 ° C in order to complete the MgO-Si0 2 glass film on the surface.
  • hydrogen gas is used as the atmospheric gas.
  • This method is inadequate if, for example, aluminum nitride is used as an inhibitor to improve the magnetic properties of the steel (nitride variant).
  • This type of steel sheet is produced by a process which carries out the decarburization at an intermediate thickness or intermediate thickness (and not at the final thickness as with the sulfide variant) and which involves a slow heating (5 - 15 ° C / hour) in the temperature range primary recrystallization (400 - 700 ° C) required.
  • the thickness of the faience layer Si0 2 -FeO
  • the quality of the forsterite base layer is deteriorated, even if subsequent annealing is carried out in the inert gas atmosphere. This occurs particularly at the edges where there is a temperature gradient, there is an increase in the inter-winding gap and the water vapor is removed before the formation process of the forsterite layer begins.
  • the iron thus formed in the oxide layer has a negative effect on the formation of the forsterite base layer.
  • the conditions for the formation of the base layer improve significantly when the iron oxides of the fayalite are converted by silicon metal according to the following relationship:
  • the object of the present invention is therefore to provide a method for producing a forsterite insulation film on a surface of grain-oriented anisotropic electrotechnical steel sheets, in particular for steels of the nitride variant, with good adhesion and at the same time high quality of the magnetic properties.
  • the invention is based on the idea of adjusting the moisture (dew point temperature) of the furnace atmosphere during slow heating from 400 to 800 ° C. to 900 ° C. (temperature of the active formation of the base layer) by increasing the oxidation potential, hydrogen being replaced by nitrogen.
  • the present invention is particularly for steel sheets with 0.8 to 3.5% Si, 0.003 to 0.055% C, 0.10 to 0.30% Mn, 0.003 to 0.020% S, 0.010 to 0.025% Al, 0.0006 to 0.01% N 2 and 0.06 to 0.6% Cu applicable with excellent results.
  • the required magnetic properties for such steels can be obtained by using a method with a two-stage cold rolling procedure and an intermediate decarburization annealing (preferably in the thickness of 0.65 to 0.75 mm).
  • Reduction rate of over 50% thins the film so that it is necessary to thicken the fayalite film by oxidation before the formation of the forsterite layer during high-temperature annealing.
  • the above-mentioned conditions determine the lower limit of the dew point range, which is set according to the invention when nitrogen is added to the furnace, to -10 ° C. Below this temperature, the thickness of the fayalite that forms is not sufficient.
  • the dew point is above + 10 ° C with humidified nitrogen and above + 20 ° C with humidified hydrogen, a very intensive oxidation results in an excessively thick coating with poor adhesion and a poor surface appearance.
  • the batch factor or fill factor of the finished product then deteriorates.
  • the common feature of the present invention and the known solution indicated above is thus the increase in the oxidation potential of the atmosphere in order to prevent the restoration or reconstruction of fayalite by hydrogen in the high-temperature annealing stage.
  • the solution according to the invention achieves this by changing the composition of the gases introduced, by the degree of hydration of MgO and by adding substances which dissociate with hydroxide precipitates at temperatures of 600 to 900 ° C., for example MgS0 4 , CaS0 4 , (NH 3 ) 2 S0, for example according to the relationships: 8th
  • MgO + MgS0 4 MgO + S0 2 + H 2 0 (3)
  • the dew point temperature is set to a value between -10 ° C and +10 ° C when nitrogen is introduced as an inert gas into the furnace atmosphere.
  • the dew point temperature is set to a value between +5 ° C and +20 ° C when hydrogen is introduced.
  • the moisture in the inter-winding space is adjusted within the limits of 5 to 20% by changing the degree of hydration of MgO.
  • the moisture in the winding interspace is additionally adjusted by adding components to the MgO which dissociate in the range from 600 to 900 ° C. and release H 2 O.
  • the end faces of the coil are thermally insulated.
  • the combination of the above features according to the present invention provides a forsterite film with good adhesion and surface appearance for steel sheets with high magnetic quality.
  • Hot rolled strips were subjected to a pickling treatment, two cold rolling steps and an intermediate decarburization with a thickness of 0.7 mm.
  • the final thickness (0.30 mm) sheet was coated with the MgO slurry at a hydration rate of 2-20%, with or without the addition of MgS0 (0.4 to 1.2 grams / liter) and in a coil wound.
  • the coil was annealed in accordance with the conditions of the prototype process specified above and in accordance with the process proposed according to the invention and with deviations from the process proposed according to the invention.
  • the heating rate for the high temperature annealing within the temperature range of 400 to 650 ° C was 5 to 15 ° C / hour.
  • the temperature conditions and the results of the insulation layer obtained are shown in the table.
  • the optimal combination of parameters ensures high-quality magnetic properties and perfect quality of the forsterite layer (e.g. table, experiment no. 2 - 9).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

L'invention concerne un procédé permettant de produire un film d'isolation en forstérite sur la surface de tôles d'acier à grains orientés et électrotechniquement anisotropes. Ce procédé consiste à réaliser le recuit de recarbonisation d'une tôle d'acier afin de produire un film de SiO>2<-FeO-Fayalite à sa surface; à revêtir la tôle d'acier de MgO; à enrouler la tôle d'acier d'épaisseur finale et recouverte de MgO; à réaliser le recuit à température élevée de la tôle d'acier d'épaisseur finale et enroulée dans une atmosphère d'une composition prédéterminée afin de former un film de forstérite. Le procédé est notamment caractérisé en ce qu'à l'étape de recuit à haute température, on réalise un échauffement de la tôle d'acier enroulée dans la plage de températures comprise entre 400 et 800 DEG C dans une atmosphère humide contenant de l'hydrogène et/ou un gaz inerte et oxydant le fer et le silicium. La température du point de condensation au moins au niveau de la valeur limite supérieure de cette plage de températures est réglée à une valeur comprise entre -10 DEG C et +20 DEG C en fonction du rapport hydrogène/gaz inerte.
PCT/EP1999/002394 1998-04-09 1999-04-08 Procede permettant de produire un film d'isolation en forsterite sur la surface de toles d'acier a grains orientes et electrotechniquement anisotropes Ceased WO1999053107A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19816200.6 1998-04-09
DE19816200A DE19816200A1 (de) 1998-04-09 1998-04-09 Verfahren zur Herstellung eines Forsterit-Isolationsfilms auf einer Oberfläche von korn-orientierten, anisotropen, elektrotechnischen Stahlblechen

Publications (1)

Publication Number Publication Date
WO1999053107A1 true WO1999053107A1 (fr) 1999-10-21

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PCT/EP1999/002394 Ceased WO1999053107A1 (fr) 1998-04-09 1999-04-08 Procede permettant de produire un film d'isolation en forsterite sur la surface de toles d'acier a grains orientes et electrotechniquement anisotropes

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DE (1) DE19816200A1 (fr)
WO (1) WO1999053107A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3693496A1 (fr) 2019-02-06 2020-08-12 Rembrandtin Lack GmbH Nfg.KG Composition aqueuse destinée au revêtement d'acier à grains orientés

Citations (11)

* Cited by examiner, † Cited by third party
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US3930906A (en) * 1974-02-28 1976-01-06 Kawasaki Steel Corporation Method for forming an insulating glass film on a grain-oriented silicon steel sheet having a high magnetic induction
US4127429A (en) * 1976-07-05 1978-11-28 Kawasaki Steel Corporation Forsterite insulating films formed on surface of a grain-oriented silicon steel sheet having a high magnetic induction and a method of forming the same
JPS55110726A (en) * 1979-11-06 1980-08-26 Kawasaki Steel Corp Formation of insulating film on high-magnetic flux density grain-oriented silicone steel plate
US4268326A (en) * 1978-06-09 1981-05-19 Nippon Steel Corporation Process for producing grain oriented electrical silicon steel sheet
US4698272A (en) * 1985-02-22 1987-10-06 Kawasaki Steel Corporation Extra-low iron loss grain oriented silicon steel sheets
US5223048A (en) * 1988-10-26 1993-06-29 Kawasaki Steel Corporation Low iron loss grain oriented silicon steel sheets and method of producing the same
JPH0610050A (ja) * 1992-06-26 1994-01-18 Kawasaki Steel Corp 磁気特性の優れた一方向性けい素鋼板の製造方法
EP0589418A1 (fr) * 1992-09-21 1994-03-30 Nippon Steel Corporation Procédé pour la production d'une tôle d'acier à grains orientés ayant une couche primaire réduite au minimum, des propriétés magnétiques excellentes et bonne ouvrabilité
US5507883A (en) * 1992-06-26 1996-04-16 Nippon Steel Corporation Grain oriented electrical steel sheet having high magnetic flux density and ultra low iron loss and process for production the same
US5665178A (en) * 1995-02-13 1997-09-09 Kawasaki Steel Corporation Method of manufacturing grain-oriented silicon steel sheet having excellent magnetic characteristics
US5685920A (en) * 1994-05-13 1997-11-11 Nippon Steel Corporation Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same

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US2394047A (en) * 1941-07-24 1946-02-05 Westinghouse Electric Corp Process of coating ferrous silicon magnetic material
GB572491A (en) * 1944-01-25 1945-10-10 George Raymond Shepherd Improved method of treating sheets of ferrous silicon magnetic material to produce an electrically insulating film on the surfaces of the sheet
US2543710A (en) * 1948-01-15 1951-02-27 Westinghouse Electric Corp Process for producing insulating iron oxide coatings
US3116179A (en) * 1960-09-27 1963-12-31 Armco Steel Corp Production of non-oriented ferrous magnetic materials
US3544396A (en) * 1967-08-28 1970-12-01 Armco Steel Corp Silicon steel coated with magnesia containing chromic oxide
JPS4813814B1 (fr) * 1969-12-18 1973-05-01
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US3945862A (en) * 1973-06-26 1976-03-23 Merck & Co., Inc. Coated ferrous substrates comprising an amorphous magnesia-silica complex
JPS5466935A (en) * 1977-11-09 1979-05-29 Kawasaki Steel Co Method of forming forsterite insulating layer in directive silicon steel plate
JPS54143718A (en) * 1978-04-28 1979-11-09 Kawasaki Steel Co Formation of insulating layer of directional silicon steel plate
JPS60145382A (ja) * 1984-01-09 1985-07-31 Nippon Steel Corp 磁気特性、皮膜特性とも優れた方向性電磁鋼板の製造方法
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930906A (en) * 1974-02-28 1976-01-06 Kawasaki Steel Corporation Method for forming an insulating glass film on a grain-oriented silicon steel sheet having a high magnetic induction
US4127429A (en) * 1976-07-05 1978-11-28 Kawasaki Steel Corporation Forsterite insulating films formed on surface of a grain-oriented silicon steel sheet having a high magnetic induction and a method of forming the same
US4268326A (en) * 1978-06-09 1981-05-19 Nippon Steel Corporation Process for producing grain oriented electrical silicon steel sheet
JPS55110726A (en) * 1979-11-06 1980-08-26 Kawasaki Steel Corp Formation of insulating film on high-magnetic flux density grain-oriented silicone steel plate
US4698272A (en) * 1985-02-22 1987-10-06 Kawasaki Steel Corporation Extra-low iron loss grain oriented silicon steel sheets
US5223048A (en) * 1988-10-26 1993-06-29 Kawasaki Steel Corporation Low iron loss grain oriented silicon steel sheets and method of producing the same
JPH0610050A (ja) * 1992-06-26 1994-01-18 Kawasaki Steel Corp 磁気特性の優れた一方向性けい素鋼板の製造方法
US5507883A (en) * 1992-06-26 1996-04-16 Nippon Steel Corporation Grain oriented electrical steel sheet having high magnetic flux density and ultra low iron loss and process for production the same
EP0589418A1 (fr) * 1992-09-21 1994-03-30 Nippon Steel Corporation Procédé pour la production d'une tôle d'acier à grains orientés ayant une couche primaire réduite au minimum, des propriétés magnétiques excellentes et bonne ouvrabilité
US5685920A (en) * 1994-05-13 1997-11-11 Nippon Steel Corporation Annealing separator having excellent reactivity for grain-oriented electrical steel sheet and method of use the same
US5665178A (en) * 1995-02-13 1997-09-09 Kawasaki Steel Corporation Method of manufacturing grain-oriented silicon steel sheet having excellent magnetic characteristics

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Also Published As

Publication number Publication date
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