EP0619376B1 - Method for manufacturing grain oriented electrical sheets with improved core loss - Google Patents

Method for manufacturing grain oriented electrical sheets with improved core loss Download PDF

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Publication number
EP0619376B1
EP0619376B1 EP94103908A EP94103908A EP0619376B1 EP 0619376 B1 EP0619376 B1 EP 0619376B1 EP 94103908 A EP94103908 A EP 94103908A EP 94103908 A EP94103908 A EP 94103908A EP 0619376 B1 EP0619376 B1 EP 0619376B1
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Prior art keywords
temperature
hot
strip
slabs
rolled
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EP94103908A
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German (de)
French (fr)
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EP0619376A1 (en
Inventor
Fritz Dr. Dipl.-Phys. Bölling
Andreas Dr. Dipl.-Phys. Böttcher
Manfred Dr. Dipl.-Ing. Espenhahn
Christof Dipl.-Phys. Holzapfel
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Thyssen Stahl AG
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Thyssen Stahl AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C21D8/1205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular fabrication or treatment of ingot or slab
    • 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
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
    • 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
    • C21D8/1261—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 following hot rolling
    • 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
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • C21D3/04—Decarburising
    • 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
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1233—Cold rolling

Definitions

  • the invention relates to a process for the production of grain-oriented electrical sheets with a finished strip thickness in the range from 0.1 to 0.5 mm, in which more than 0.005% to 0.10% C, 2.5 to 6%, produced by continuous casting, Slabs containing 5% Si and 0.03 to 0.15% Mn are first heated through at a reduced temperature in one or two stages and then pre-rolled and hot-rolled to the final hot strip thickness, and then the strips hot-rolled to the final thickness are annealed and cooled in an accelerated manner and cold-rolled to the finished strip thickness in a cold-rolling stage or in a plurality of cold-rolling stages, and the cold-rolled strips are then subjected to recrystallizing annealing in a humid H 2 and N 2 atmosphere with simultaneous decarburization, and the application of an essentially MgO-containing release agent to both sides of the cold strip surface , a high temperature annealing and finally a final annealing with an insulation b be subjected to stratification.
  • Slabs preferably continuous cast slabs with a thickness in the range of approximately 150 to 250 mm, which is usually 0.025 up to 0.085% C and 2.0 to 4.0% Si as well as manganese, sulfur, possibly Contain aluminum and nitrogen before hot rolling in one or in two stages to a temperature of the order of magnitude from 1350 ° C to max.
  • This measure serves the purpose of being used as grain growth inhibitors known and as the control phase in high-temperature annealing (Secondary recrystallization) acting particles, e.g. Sulfides (MnS) and nitrides (AlN), completely dissolved.
  • the second heating stage up to a temperature of max. 1450 ° C and one Warm the slabs at this temperature to then the slabs already reduced in thickness to hot strip with a final thickness in the range of 1.5 to approx. 5 mm, max. to Roll 7 mm warm and finished.
  • DE-C2 29 09 500 describes a process for the production known from grain-oriented electrical sheets, in which the slabs containing 2.0 to 4.0% Si, up to 0.085% C and up to Contain 0.065% Al or another known inhibitor, before hot rolling in one step to a temperature of at least 1300 ° C, preferably greater than 1350 ° C, heated and heated through at this temperature, i.e. a sufficient time be kept long. This should prevent the inhibitors from Hot rolling completely dissolved and not eliminated prematurely to prevent the hot rolling from large and coarse excretions arise.
  • An excretion of the inhibitors also during the subsequent one Avoiding hot rolling is accordingly known in this Process provided that the hot rolling at least one recrystallization rolling during finish rolling with at least a stitch decrease of more than 30% in a temperature range from 960 ° C to 1190 ° C, namely expressis verbis with the Provided that the inhibitors do not fail during hot rolling. Elimination of the inhibitors and especially one Coarsening of the particles that may have been excreted are subsequently this known method preferably avoided 'when the recrystallization rolling of the previously at a temperature of at least 1350 ° C through heated slabs in the temperature range from 1050 ° C to 1150 ° C is carried out.
  • the slabs are made in the usual way Hot-rolled, the hot-rolled strip is heat-treated or annealed and then also in a conventional manner in one step or cold rolled to the final sheet thickness in two stages.
  • the cold-rolled strip is then annealed for decarburization Connect a release agent to both sides of the cold strip surface applied and finally a high temperature annealing subjected to secondary recrystallization.
  • (Si, Al) N particles are apparently only used as inhibitors effective or the grain-oriented electrical sheets with the desired magnetic properties can only be produced when the cold rolled strip at the end of primary recrystallization and decarburization annealing and before introduction secondary recrystallization of nitriding, i.e. one additional further process step is subjected.
  • S can contain aluminum nitrides during solution treatment of the Slabs can only be brought into solution incompletely.
  • the necessary Inhibitors are therefore used after decarburization annealing - As in the known from EP-B1 0 219 611 Process - by embroidery or nitriding of the tape. This can be done by setting, for example a special ammonia-containing gas atmosphere after the Decarburization annealing and before high temperature annealing and / or by adding nitrogen-containing compounds to the im essential release agents containing MgO (e.g. according to EP-A1 0 339 474, EP-A1 0 390 142).
  • EP-B1 0 098 324 and EP-A2 0 392 535 known in which the heating temperature is below 1280 ° C and an additional process step, e.g. the Nitriding, is not absolutely necessary.
  • Stabilizing the According to EP-A2 0 392 535, secondary recrystallization is carried out by Setting the hot rolling parameters, such as final hot rolling temperature, Degree of deformation (based on the last three hot rolling passes) or reel temperature reached. Following EP-B1 0 098 324 this stabilization will be achieved through the coordination of the Annealing conditions that reach hot rolling and cold rolling parameters.
  • the object of the invention is to improve the method of the type mentioned at the outset with the advantageously reduced temperature for the solution annealing of the slabs in such a way that for the magnetic properties of the electrical sheets, in particular for the magnetic reversal losses P 1.7 / 50 , more favorable values can be achieved without using further process steps.
  • this object is achieved in the method of the beginning mentioned type through the measures and procedural steps (1) to (4) of claim 1 solved.
  • the slabs in addition to the usual nitrogen content in the range of 0.0045 to 0.0120% additionally 0.020 to 0.300% Cu and more than Contain 0.010% S, but less than 0.035% Al.
  • the method steps (2) and (3) that manganese sulfides are practically not brought into solution and therefore mostly as coarse after hot rolling Particles are present.
  • RGO Regular Grain Oriented
  • the invention By heating the slabs according to (2) that aluminum nitrides only to a small extent be brought into solution and therefore also predominantly after hot rolling according to (3) excreted as coarse particles. This one too Share can no longer in the subsequent procedural steps act as an inhibitor.
  • HGO High-permeability Grain Oriented
  • crucial grain growth inhibitor Precipitated copper-sulfide particles are with an average diameter of less than about 100 nm, preferably less than 50 nm, in the following Stages or procedural steps the actual, essential and represent effective tax phase. Only one more small proportion after the process step according to the invention (4) also separated and finely divided aluminum nitrides effective as an inhibitor. This is particularly evident non-inventive comparative examples by the inventive Procedure with otherwise identical features and procedural steps is applied to slabs, but only one Have a sulfur content of less than 0.005%. In these cases there are no sufficient particles acting as inhibitors large number before.
  • the slabs contain approx. 0.010 to 0.065% Al
  • the slabs also before the hot rolling at a temperature of the order of magnitude of about 1400 ° C, are hot inhibitors by the hot rolling and subsequent hot strip annealing are finely divided AlN particles and such electrical sheets preferably have a magnetic induction B 8 greater than 1.88 T.
  • grain-oriented electrical sheets can now be produced using the method according to the invention with the same magnetic induction B 8 in Tesla (T) as RGO and also HGO electrical sheets have with improved values for the magnetic loss P 1.7 / 50 in watts per kg (W / kg).
  • the method of the invention are first of all with the help of the known continuous casting process slabs with an initial thickness in the range of 150 to 300 mm, preferably in the Range from 200 to 250 mm.
  • the Slabs also known as thin slabs with an initial thickness in be in the range of approximately 30 to 70 mm.
  • Advantageously can be used in these cases during the production of the hot strip the process step (3) on the roughing to an intermediate thickness to be dispensed with.
  • Grain-oriented electrical sheets can also be used by the process according to the invention also from slabs or tapes with an even smaller starting thickness if using these slabs or tapes beforehand of the strip casting were generated.
  • the slabs, thin slabs or strips, hereinafter briefly slabs named and so defined contain the in the preamble and in characterizing part of claim 1 specified content of carbon, silicon, manganese, nitrogen and copper as well compared to the prior art (according to EP-B1 0 219 611) the sulfur content according to the invention in the range from more than 0.010, preferably greater than 0.015%, up to 0.050% and the one specifically lowered into the lower known area Aluminum content in the range from 0.010 to 0.030%, max. up to 0.035%, balance Fe including impurities.
  • the contents specified in claim 2 adjusted to aluminum and sulfur.
  • the salary too the remaining alloy components are preferably for each Alloy element individually or in combination within the areas specified in claim 2.
  • composition tin up to 0.15%, but preferably only 0.02-0.06%, be added. This will make the magnetic properties not further improved.
  • Figures 1, 2 and 3 illustrate the solution behavior for grain-oriented electrical sheets with usual Si contents. The contents taken into account correspond to the exemplary embodiments shown in Tables 1, 2 and 3.
  • Carrying out process step (2) causes that heating of the slabs before hot rolling manganese sulfides practically cannot be brought into solution. Because the corresponding Solubility curves for aluminum nitride the solubility curves are similar or comparable for manganese sulfides already in the heating of the slabs according to the invention the majority of aluminum nitrides excreted. After completing this step practically only copper sulfides are almost completely in solution.
  • Method step (3) may be dependent first from the initial thickness of the slabs in 3 to 7 stitches pre-rolled and then in 5 to 9 passes to the final hot strip thickness in the range from 1.5 to 5 mm, max. up to 7 mm finish rolled.
  • the slabs are pre-rolled with a Initial thickness in the range of 150 to 300 mm, preferably in the range from 200 to 250 mm, except for a pre-strip thickness in the range of approx. 30 to 60 mm. Overall, the number of Stitches during roughing and finish rolling according to the starting thickness of the slabs and according to the desired one Final hot strip thickness.
  • the essential feature of process step (3) is, however, that the strips with the lowest possible final rolling temperature in the range of 880 ° C to 1000 ° C, preferably in the range from 900 ° C to 980 ° C.
  • the lower limit determined by the fact that there is still a problem-free deformation or rolling the strips without any difficulties, such as. Strip unevenness and strip profile deviations, must be possible.
  • Hot rolling is more than 60% of the total nitrogen content bound to aluminum in the form of AlN.
  • a Measure of the amount of nitrogen present in aluminum is the N-Beeghley value.
  • Table 4 illustrates how the invention Process the type and size of the excretions, and thus their Effectiveness as an inhibitor. It also shows the differences from the present excretions, the achieved by methods according to the state of the art (HGO, RGO) will.
  • cold rolling takes place the tapes preferably in one step to the finished tape thickness in the range of 0.1 to 0.5 mm.
  • the final hot strip thickness can be cold rolled according to claim 6 also take place in two stages, according to claim 7 before the first cold rolling stage is preferably preheated becomes. This contributes to stabilization in an advantageous manner secondary recrystallization in the subsequent high-temperature annealing at.
  • the recrystallizing and decarburizing annealing of the strips is carried out at a temperature in the range from 750 ° C. to 900 ° C., preferably at a temperature in the range from 820 ° C. to 880 ° C, in a humid atmosphere containing H 2 and N 2 .
  • a glow separator containing primarily MgO is then applied.
  • the strips are then in a known manner in a long-term hood annealing with a slow heating of 10 to 100 K / h, preferably 15 to 25 K / h, to at least 1150 ° C at this temperature in an atmosphere consisting of H 2 and N 2 annealed and slowly cooled again after holding for 0.5 to 30 h.
  • the insulation coating which is also known, is carried out with the associated final annealing.
  • Table 1 shows the results using eight exemplary embodiments when using the method according to the invention Claim 1 on slabs with an initial thickness of 215 mm.
  • Table 2 shows further results, that according to the inventive method according to claim 1 in combination with the procedural steps according to the subclaims 6 and 7 can be achieved.
  • the cold rolling took place in these cases in two stages without and also with the preheating before the first cold rolling stage according to claim 7.
  • grain-oriented electrical sheets can be produced which have a magnetic induction B 8 , as they also have grain-oriented electrical sheets of both the RGO grade and the HGO grade.
  • these grades are now only achieved by using a single method with the method steps specified in claim 1.
  • values which are substantially more favorable for the associated magnetic reversal losses are advantageously achieved. This is illustrated in FIG.
  • FIG. 4 shows the corresponding and typical value pairs for grain-oriented electrical sheets of the RGO and HGO grades, which until now could only be produced in a known manner using two separate, different processes.

Abstract

A process for the production of grain oriented magnetic steel sheets comprises through-heating slabs containing more than 0.005% C, 2.5 to 6.5% Si, 0.03 to 0.15% Mn, 0.010 to 0.050% S, 0.010 to 0.035% Al, 0.0045 to 0.0120% N, and 0.020 to 0.300% Cu, the balance being iron and residual impurities, to a temperature which is lower than the solubility temperature T1 of magnesium sulfide and higher than the solubility temperature T2 of copper sulfide, T1 and T2 being dependent on the silicon content. The through-heated slabs are then hot roughed, followed by hot finish rolling at an initial temperature of at least 960 DEG C. and a final rolling temperature of 880 DEG C. to 1,000 DEG C., to produce a hot rolled strip having a thickness in the range of 1.5 to 7 mm. During this last step, at least 60% of the total nitrogen content precipitates in the form of coarse AlN particles. Thereafter, the hot rolled strips are annealed at temperature of 880 DEG C. to 1,150 DEG C., followed by cooling at a cooling rate higher than 15 DEG K./sec to induce further precipitation of AlN and copper sulfide particles. Thereafter the strip is cold rolled in one or more cold rolling stages to a final strip thickness of 0.1 mm to 0.5 mm, subjected to recrystallization and decarburization annealing in a wet atmosphere containing H2 and N2. A separating agent containing mainly MgO is then applied to both surfaces of the strip. The strip is then high temperature annealed, an insulating coating is applied and the strip is subjected to a final annealing.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von kornorientierten Elektroblechen mit einer Fertigbanddicke in dem Bereich von 0,1 bis 0,5 mm, bei dem durch ein Stranggießen erzeugte, mehr als 0,005 % bis 0,10 % C, 2,5 bis 6,5 % Si und 0,03 bis 0,15 % Mn enthaltende Brammen zunächst bei einer abgesenkten Temperatur in ein oder zwei Stufen durcherwärmt und anschließend bis auf Warmband-Enddicke warm vor- und fertiggewalzt werden, im Anschluß daran die bis auf Enddicke warmgewalzten Bänder geglüht und beschleunigt abgekühlt sowie in einer Kaltwalzstufe oder in mehreren Kaltwalzstufen bis auf die Fertigbanddicke kaltgewalzt werden und die kaltgewalzten Bänder sodann einer rekristallisierenden Glühung in feuchter H2 und N2 enthaltenden Atmosphäre mit gleichzeitiger Entkohlung, dem Aufbringen eines im wesentlichen MgO enthaltenden Trennmittels beidseitig auf die Kaltbandoberfläche, einer Hochtemperaturglühung und schließlich einer Schlußglühung mit einer Isolationsbeschichtung unterworfen werden.The invention relates to a process for the production of grain-oriented electrical sheets with a finished strip thickness in the range from 0.1 to 0.5 mm, in which more than 0.005% to 0.10% C, 2.5 to 6%, produced by continuous casting, Slabs containing 5% Si and 0.03 to 0.15% Mn are first heated through at a reduced temperature in one or two stages and then pre-rolled and hot-rolled to the final hot strip thickness, and then the strips hot-rolled to the final thickness are annealed and cooled in an accelerated manner and cold-rolled to the finished strip thickness in a cold-rolling stage or in a plurality of cold-rolling stages, and the cold-rolled strips are then subjected to recrystallizing annealing in a humid H 2 and N 2 atmosphere with simultaneous decarburization, and the application of an essentially MgO-containing release agent to both sides of the cold strip surface , a high temperature annealing and finally a final annealing with an insulation b be subjected to stratification.

Zur Herstellung von kornorientierten Elektroblechen ist es bekannt, Brammen, vorzugsweise Stranggußbrammen mit einer Dicke in dem Bereich von ca. 150 bis 250 mm, die üblicherweise 0,025 bis 0,085 % C und 2,0 bis 4,0 % Si sowie Mangan, Schwefel, ggf. Aluminium und Stickstoff enthalten, vor dem Warmwalzen in einer oder in zwei Stufen auf eine Temperatur in der Größenordnung von 1350°C bis max. 1450°C zu erwärmen und bei dieser Temperatur eine hinreichende Zeit lang zu halten (durchzuerwärmen), um eine homogene Durcherwärmung der Brammen sicherzustellen. Diese Maßnahme dient dem Zweck, die als Kornwachstums-Inhibitoren bekannten und als Steuerphase bei der Hochtemperaturglühung (Sekundär-Rekristallisation) wirkenden Teilchen, wie z.B. Sulfide (MnS) und Nitride (AlN), vollständig in Lösung zu bringen.For the production of grain-oriented electrical sheets, it is known Slabs, preferably continuous cast slabs with a thickness in the range of approximately 150 to 250 mm, which is usually 0.025 up to 0.085% C and 2.0 to 4.0% Si as well as manganese, sulfur, possibly Contain aluminum and nitrogen before hot rolling in one or in two stages to a temperature of the order of magnitude from 1350 ° C to max. To heat 1450 ° C and at this temperature to hold (warm up) for a sufficient time, to ensure homogeneous heating of the slabs. This measure serves the purpose of being used as grain growth inhibitors known and as the control phase in high-temperature annealing (Secondary recrystallization) acting particles, e.g. Sulfides (MnS) and nitrides (AlN), completely dissolved.

Um insbesondere bei der zweistufigen Erwärmung und Durcherwärmung bzw. Lösungsglühung der Brammen einem zu starken Wachstum der Körner und damit einer daraus resultierenden unvollständigen sekundären Rekristallisation bei der Hochtemperaturglühung entgegenzuwirken, ist es ferner bekannt (DE-C3 22 52 784, DE-B2 23 16 808), zwischen der ersten und zweiten Stufe ein als "Pre-Rolling" (Zwischenwalzen) bekanntes Vorwalzen vorzusehen. Dabei werden die zunächst nur auf eine Temperatur von ca. 1200°C bis 1300°C erwärmten Brammen nach dieser ersten Stufe mit einem auf ihre Dicke bezogenen Reduktionsgrad bzw. mit einer Querschnittsabnahme von 30 bis 70 % gewalzt, um beispielsweise mehr als 80 % der Körner auf einen mittleren Durchmesser von max. 25 mm einzustellen. Im Anschluß daran schließen sich zum Lösen der Mangansulfide und der Aluminiumnitride die zweite Erwärmungsstufe bis auf eine Temperatur von max. 1450°C und eine Durcherwärmung der Brammen bei dieser Temperatur an, um sodann die bereits in ihrer Dicke reduzierten Brammen zu Warmband mit einer Enddicke in dem Bereich von 1,5 bis ca. 5 mm, max. bis 7 mm warm vor- und fertig zu walzen. Especially when it comes to two-stage heating and heating or solution annealing of the slabs a too strong growth the grains and thus a resulting incomplete one secondary recrystallization in high temperature annealing counteract, it is also known (DE-C3 22 52 784, DE-B2 23 16 808), between the first and second stage as "pre-rolling" (Intermediate rolling) to provide known roughing. Here are initially only at a temperature of approx. 1200 ° C to After this first stage, 1300 ° C heated slabs with one their thickness related degree of reduction or with a decrease in cross-section rolled from 30 to 70%, for example more than 80% of the grains to an average diameter of max. 25 mm. Then close to release the manganese sulfide and the aluminum nitride the second heating stage up to a temperature of max. 1450 ° C and one Warm the slabs at this temperature to then the slabs already reduced in thickness to hot strip with a final thickness in the range of 1.5 to approx. 5 mm, max. to Roll 7 mm warm and finished.

Andererseits ist aus der DE-C2 29 09 500 ein Verfahren zur Herstellung von kornorientierten Elektroblechen bekannt, bei dem die Brammen, die 2,0 bis 4,0 % Si, bis zu 0,085 % C und bis zu 0,065 % Al oder einen anderen bekannten Inhibitor enthalten, vor dem Warmwalzen in nur einer Stufe bis auf eine Temperatur von mindestens 1300°C, vorzugsweise größer 1350°C, erwärmt und bei dieser Temperatur durcherwärmt, d.h. eine hinreichende Zeit lang gehalten werden. Dadurch sollen die Inhibitoren vor dem Warmwalzen vollständig aufgelöst und nicht schon vorzeitig ausgeschieden werden, um zu verhindern, daß beim Warmwalzen zu große und grobe Ausscheidungen entstehen. Um eine Ausscheidung der Inhibitoren auch während des sich daran anschließenden Warmwalzens zu vermeiden, ist demgemäß bei diesem bekannten Verfahren vorgesehen, daß das Warmwalzen mindestens ein Rekristallisationswalzen während des Fertigwalzens mit mindestens einer Stichabnahme von mehr als 30 % in einem Temperaturbereich von 960°C bis 1190°C enthält, und zwar expressis verbis mit der Maßgabe, daß die Inhibitoren während des Warmwalzens nicht ausfallen. Eine Ausscheidung der Inhibitoren und insbesondere eine Vergröberung der ggf. doch ausgeschiedenen Teilchen werden nach diesem bekannten Verfahren vorzugsweise dann vermieden', wenn das Rekristallisationswalzen der zuvor bei einer Temperatur von mindestens 1350°C durcherwärmten Brammen in dem Temperaturbereich von 1050°C bis 1150°C durchgeführt wird.On the other hand, DE-C2 29 09 500 describes a process for the production known from grain-oriented electrical sheets, in which the slabs containing 2.0 to 4.0% Si, up to 0.085% C and up to Contain 0.065% Al or another known inhibitor, before hot rolling in one step to a temperature of at least 1300 ° C, preferably greater than 1350 ° C, heated and heated through at this temperature, i.e. a sufficient time be kept long. This should prevent the inhibitors from Hot rolling completely dissolved and not eliminated prematurely to prevent the hot rolling from large and coarse excretions arise. An excretion of the inhibitors also during the subsequent one Avoiding hot rolling is accordingly known in this Process provided that the hot rolling at least one recrystallization rolling during finish rolling with at least a stitch decrease of more than 30% in a temperature range from 960 ° C to 1190 ° C, namely expressis verbis with the Provided that the inhibitors do not fail during hot rolling. Elimination of the inhibitors and especially one Coarsening of the particles that may have been excreted are subsequently this known method preferably avoided 'when the recrystallization rolling of the previously at a temperature of at least 1350 ° C through heated slabs in the temperature range from 1050 ° C to 1150 ° C is carried out.

Insbesondere im Falle von Al enthaltenden Brammen verursachen ihre einstufige Durcherwärmung bei einer abgesenkten Temperatur und zusätzlich das Warmwalzen in einem ebenfalls abgesenkten Temperaturbereich eine Ausfällung und Vergröberung von Aluminiumnitrid mit dem Ergebnis, daß die sekundäre Rekristallisation in den sich daran anschließenden Stufen bzw. Verfahrensschritten unvollständig ist. Dies führt zu schlechten magnetischen Eigenschaften der in dieser Weise hergestellten kornorientierten Elektrobleche. Trotz dieses Hinweises in der DE-C2 29 09 500 wird bei dem aus der EP-B1 0 219 611 bekannten Verfahren zur Herstellung von kornorientierten Elektroblechen, von dem die Erfindung ausgeht, vorgeschlagen, die Brammen vor dem Warmwalzen, d.h. vor dem Vor- und Fertigwalzen, auf eine Temperatur von in jedem Fall größer 1000°C bis zu max. 1270°C zu erwärmen und bei dieser Temperatur durchzuerwärmen. Dabei enthalten die Brammen 1,5 bis 4,5 % Si sowie gemäß den Ausführungsbeispielen die üblichen Gehalte an Kohlenstoff, Mangan, Aluminium und Stickstoff, jedoch vorzugsweise nur einen Schwefelgehalt von weniger als 0,007 %.Especially in the case of slabs containing Al, their single-stage heating at a reduced temperature and, in addition, hot rolling in a likewise reduced temperature range cause precipitation and coarsening of aluminum nitride with the result that the secondary recrystallization in the subsequent stages or process steps is incomplete. This leads to poor magnetic properties of the grain-oriented electrical sheets produced in this way. Despite this reference in DE-C2 29 09 500, it is proposed in the process known from EP-B1 0 219 611 for the production of grain-oriented electrical sheets, from which the invention is based, that the slabs before hot rolling, ie before and before and Finishing rolls, to a temperature of in any case greater than 1000 ° C up to max. To heat 1270 ° C and to heat at this temperature. The slabs contain 1.5 to 4.5% Si and, according to the exemplary embodiments, the usual contents of carbon, manganese, aluminum and nitrogen, but preferably only a sulfur content of less than 0.007%.

Bei diesem bekannten Verfahren werden die Brammen in üblicher Weise warmgewalzt, das warmgewalzte Band wärmebehandelt bzw. geglüht und dann ebenfalls in an sich bekannter Weise einstufig oder zweistufig auf die endgültige Blechdicke kaltgewalzt. Das kaltgewalzte Band wird anschließend zur Entkohlung geglüht, im Anschluß daran ein Trennmittel beidseitig auf die Kaltbandoberfläche aufgetragen und schließlich einer Hochtemperaturglühung zur sekundären Rekristallisation unterworfen. Die bei Anwendung dieses Verfahrens primär auftretenden Ausscheidungen von (Si,Al)N-Teilchen werden als Inhibitor offenbar jedoch nur dann wirksam bzw. die kornorientierten Elektrobleche mit den gewünschten magnetischen Eigenschaften können nur dann hergestellt werden, wenn das kaltgewalzte Band am Ende der Primärrekristallisations- und Entkohlungsglühung und vor der Einleitung der sekundären Rekristallisation einer Nitrierung, d.h. einem zusätzlichen weiteren Verfahrensschritt, unterworfen wird.In this known method, the slabs are made in the usual way Hot-rolled, the hot-rolled strip is heat-treated or annealed and then also in a conventional manner in one step or cold rolled to the final sheet thickness in two stages. The cold-rolled strip is then annealed for decarburization Connect a release agent to both sides of the cold strip surface applied and finally a high temperature annealing subjected to secondary recrystallization. The in use excretion of However, (Si, Al) N particles are apparently only used as inhibitors effective or the grain-oriented electrical sheets with the desired magnetic properties can only be produced when the cold rolled strip at the end of primary recrystallization and decarburization annealing and before introduction secondary recrystallization of nitriding, i.e. one additional further process step is subjected.

Die Absenkung der für die Durcherwärmung bzw. Lösungsglühung der Brammen erforderlichen und in den entsprechenden Öfen einzustellenden Temperatur bedeutet in erster Linie, daß die Ausbildung von flüssiger Schlacke in diesen Öfen in vorteilhafter Weise vermieden wird. Darüber hinaus bedeutet eine solche Absenkung der Durcherwärmungstemperatur eine deutliche Energieeinsparung, wesentlich längere Ofenstandzeiten und insbesondere ein verbessertes und kostengünstigeres Ausbringen der durcherwärmten Brammen. Aus diesem Grund werden in einer Reihe von weiteren europäischen Patentanmeldungen jüngeren Datums (EP-A1 0 321 695, EP-A1 0 339 474, EP-A1 0 390 142, EP-A1 0 400 549) ebenfalls Verfahren zur Herstellung von kornorientierten Elektroblechen vorgeschlagen und zwar mit einer für die Durcherwärmung der Brammen erforderlichen Temperatur von weniger als ca. 1200°C.The lowering for the heating up or solution annealing of the slabs required and to be set in the corresponding furnaces Temperature primarily means that training of liquid slag in these furnaces is advantageous Way is avoided. In addition, such a reduction means the heating temperature a significant energy saving, much longer furnace life and in particular an improved and less expensive application of the heated ones Slabs. For this reason, a number of other recent European patent applications (EP-A1 0 321 695, EP-A1 0 339 474, EP-A1 0 390 142, EP-A1 0 400 549) likewise processes for the production of grain-oriented electrical sheets proposed and with one for warming up the temperature of the slabs is less than approx. 1200 ° C.

In den genannten Fällen, in denen die Brammen dabei vorzugsweise 0,010 bis 0,060 % Al, jedoch weniger als ca. 0,010 % S enthalten, können Aluminiumnitride bei der Lösungsglühung der Brammen nur unvollständig in Lösung gebracht werden. Die erforderlichen Inhibitoren werden daher im Anschluß an die Entkohlungsglühung - wie bei dem aus der EP-B1 0 219 611 bekannten Verfahren - durch eine Aufstickung oder auch bzw. Nitrierung des Bandes erzeugt. Dies kann beispielsweise durch die Einstellung einer besonderen ammoniakhaltigen Gasatmosphäre nach der Entkohlungsglühung und vor der Hochtemperaturglühung und/oder durch die Zugabe von stickstoffhaltigen Verbindungen zu dem im wesentlichen MgO enthaltenden Trennmittel erfolgen (z.B. gemäß EP-A1 0 339 474, EP-A1 0 390 142).In the cases mentioned, where the slabs are preferred 0.010 to 0.060% Al, but less than about 0.010% S can contain aluminum nitrides during solution treatment of the Slabs can only be brought into solution incompletely. The necessary Inhibitors are therefore used after decarburization annealing - As in the known from EP-B1 0 219 611 Process - by embroidery or nitriding of the tape. This can be done by setting, for example a special ammonia-containing gas atmosphere after the Decarburization annealing and before high temperature annealing and / or by adding nitrogen-containing compounds to the im essential release agents containing MgO (e.g. according to EP-A1 0 339 474, EP-A1 0 390 142).

Der Nachteil aller dieser bekannten Verfahren besteht darin, daß zur Erzeugung der erforderlichen Inhibitoren und damit für die Einstellung der Steuerphase vor der abschließenden Hochtemperaturglühung mindestens ein zusätzlicher weiterer Verfahrensschritt erforderlich ist. Durch zusätzliche Verfahrensschritte wird beispielsweise eine reproduzierbare Herstellung von kornorientierten Elektroblechen mit vorgegebenen gewünschten magnetischen Eigenschaften erschwert. Darüber hinaus ist die Realisierung dieser Verfahrensschritte im Produktionsablauf mit technischen Schwierigkeiten verbunden, wie z.B. die exakte Einstellung der besonderen Gasatmosphäre bei der Aufstickungs-Behandlung.The disadvantage of all of these known methods is that that to generate the necessary inhibitors and thus for the setting of the control phase before the final high-temperature annealing at least one additional process step is required. Through additional process steps For example, a reproducible production of grain-oriented Electrical sheets with predetermined desired magnetic Properties difficult. In addition, the realization of these process steps in the production process technical difficulties, such as the exact setting the special gas atmosphere during the nitriding treatment.

Aus der EP-B1 0 098 324 und der EP-A2 0 392 535 sind Verfahren bekannt, bei denen die Durcherwärmungstemperatur unter 1280°C liegt und ein zusätzlicher Verfahrensschritt, wie z.B. das Nitrieren, nicht zwingend notwendig ist. Die Stabilisierung der Sekundärrekristallisation wird gemäß EP-A2 0 392 535 durch die Einstellung der Warmwalzparameter, wie Endwarmwalztemperatur, Verformungsgrad (bezogen auf die drei letzten Warmwalzstiche) oder Haspeltemperatur erreicht. Der EP-B1 0 098 324 folgend wird diese Stabilisierung durch die Abstimmung der Glühbedingungen, der Warmwalz- und Kaltwalzparameter erreicht.Methods are known from EP-B1 0 098 324 and EP-A2 0 392 535 known in which the heating temperature is below 1280 ° C and an additional process step, e.g. the Nitriding, is not absolutely necessary. Stabilizing the According to EP-A2 0 392 535, secondary recrystallization is carried out by Setting the hot rolling parameters, such as final hot rolling temperature, Degree of deformation (based on the last three hot rolling passes) or reel temperature reached. Following EP-B1 0 098 324 this stabilization will be achieved through the coordination of the Annealing conditions that reach hot rolling and cold rolling parameters.

Keine der vorangehend genannten Schriften geht von Kupfer- und Schwefelgehalten aus, wie sie dem erfindungsgemäßen Verfahren zugrunde liegen. Elektrobleche mit einer solchen Zusammensetzung sind z.B. aus DE- A1 24 22 073 oder DE-C2 35 38 609 bekannt. Die DE-C2 32 29 295 beschreibt, daß eine Verbesserung der Eigenschaften durch die Zugabe von Zinn und Kupfer erfolgen kann. Keine der drei letztgenannten Schriften beschreibt jedoch ein Verfahren, welches die fast ausschließliche Wirkung von Kupfersulfiden als Inhibitor unterstützt oder Durcherwärmungstemperaturen kleiner 1350°C nahelegt.None of the fonts mentioned above is based on copper and Sulfur contents from how the process of the invention underlie. Electrical sheets with such a composition are e.g. known from DE-A1 24 22 073 or DE-C2 35 38 609. DE-C2 32 29 295 describes that an improvement properties by adding tin and copper can. However, none of the last three writings describes a process that uses the almost exclusive effect of Supported copper sulfides as an inhibitor or warming temperatures less than 1350 ° C suggests.

Hiervon ausgehend liegt der Erfindung die Aufgabe zugrunde, das Verfahren der eingangs genannten Art mit der in vorteilhafter Weise abgesenkten Temperatur für die Lösungsglühung der Brammen dahingehend zu verbessern, daß für die magnetischen Eigenschaften der Elektrobleche, insbesondere für die Ummagnetisierungsverluste P1,7/50, ohne Benutzung von weiteren Verfahrensschritten günstigere Werte erreicht werden.Proceeding from this, the object of the invention is to improve the method of the type mentioned at the outset with the advantageously reduced temperature for the solution annealing of the slabs in such a way that for the magnetic properties of the electrical sheets, in particular for the magnetic reversal losses P 1.7 / 50 , more favorable values can be achieved without using further process steps.

Erfindungsgemäß wird diese Aufgabe bei dem Verfahren der eingangs genannten Art durch die Maßnahmen und Verfahrensschritte (1) bis (4) des Patentanspruches 1 gelöst.According to the invention, this object is achieved in the method of the beginning mentioned type through the measures and procedural steps (1) to (4) of claim 1 solved.

Erfindungswesentlich ist gemäß (1), daß die Brammen neben dem üblichen Gehalt an Stickstoff in dem Bereich von 0,0045 bis 0,0120 % zusätzlich 0,020 bis 0,300 % Cu und mehr als 0,010 % S, jedoch weniger als 0,035 % Al enthalten. Zusätzlich dazu bewirken die erfindungsgemäßen Verfahrensschritte (2) und (3), daß Mangansulfide praktisch nicht in Lösung gebracht werden und daher bereits nach dem Warmwalzen überwiegend als grobe Teilchen ausgeschieden vorliegen. Insbesondere im Unterschied zu der konventionellen Herstellung von sogenannten RGO-Elektroblechen (RGO = Regular Grain Oriented) bedeutet dies, daß bei Anwendung des erfindungsgemäßen Verfahrens Mangansulfide als Inhibitor in den nachfolgenden Stufen bzw. Verfahrensschritten nicht wirksam werden. Ferner bewirkt die erfindungsgemäße Durcherwärmung der Brammen gemäß (2), daß Aluminiumnitride nur zu einem geringen Anteil in Lösung gebracht werden und daher nach erfolgtem Warmwalzen gemäß (3) ebenfalls überwiegend als grobe Teilchen ausgeschieden vorliegen. Auch dieser Anteil kann in den nachfolgenden Verfahrensschritten nicht mehr als Inhibitor wirksam werden.It is essential to the invention according to (1) that the slabs in addition to the usual nitrogen content in the range of 0.0045 to 0.0120% additionally 0.020 to 0.300% Cu and more than Contain 0.010% S, but less than 0.035% Al. In addition the method steps (2) and (3) that manganese sulfides are practically not brought into solution and therefore mostly as coarse after hot rolling Particles are present. Especially in the difference for the conventional production of so-called RGO electrical sheets (RGO = Regular Grain Oriented) this means that when using the method according to the invention manganese sulfides as an inhibitor in the subsequent stages or process steps do not take effect. Furthermore, the invention By heating the slabs according to (2) that aluminum nitrides only to a small extent be brought into solution and therefore also predominantly after hot rolling according to (3) excreted as coarse particles. This one too Share can no longer in the subsequent procedural steps act as an inhibitor.

Im Unterschied zu der konventionellen Herstellung von sogenannten HGO-Elektroblechen (HGO = High-permeability Grain Oriented) wird vielmehr nach Anwendung der erfindungsgemäßen Verfahrensschritte (1) bis (4) gefunden, daß entscheidender Kornwachstums-Inhibitor sehr fein verteilt ausgeschiedene Kupfer-Sulfid-Teilchen sind mit einem mittleren Durchmesser von weniger als ca. 100 nm, vorzugsweise kleiner 50 nm, die in den nachfolgenden Stufen bzw. Verfahrensschritten die eigentliche, wesentliche und wirksame Steuerphase darstellen. Nur noch zu einem sehr geringen Anteil werden nach dem erfindungsgemäßen Verfahrensschritt (4) ebenfalls ausgeschiedene und fein verteilte Aluminiumnitride als Inhibitor wirksam. Dies zeigen insbesondere nicht-erfindungsgemäße Vergleichsbeispiele, indem das erfindungsgemäße Verfahren bei sonst gleichen Merkmalen und Verfahrensschritten auf Brammen angewendet wird, die jedoch nur einen Schwefelgehalt von weniger als 0,005 % besitzen. In diesen Fällen liegen keine als Inhibitor wirkende Teilchen in genügend großer Anzahl vor.In contrast to the conventional manufacture of so-called HGO electrical sheets (HGO = High-permeability Grain Oriented) is rather after application of the method steps according to the invention (1) through (4) found that crucial grain growth inhibitor Precipitated copper-sulfide particles are with an average diameter of less than about 100 nm, preferably less than 50 nm, in the following Stages or procedural steps the actual, essential and represent effective tax phase. Only one more small proportion after the process step according to the invention (4) also separated and finely divided aluminum nitrides effective as an inhibitor. This is particularly evident non-inventive comparative examples by the inventive Procedure with otherwise identical features and procedural steps is applied to slabs, but only one Have a sulfur content of less than 0.005%. In these cases there are no sufficient particles acting as inhibitors large number before.

Im Unterschied zu dem erfindungsgemäßen Verfahren ist bei der bisherigen konventionellen Herstellung von RGO-Elektroblechen (z.B. nach der DE-A1 41 16 240) kennzeichnend, daß in diesem Fall die Brammen nur max. 0,005 % Al enthalten, diese vor dem Warmwalzen bei einer Temperatur in der Größenordnung von ca. 1400°C durcherwärmt werden, durch das Warmwalzen und durch die sich ggfs. daran anschließende Wärmebehandlung der gewalzten Bänder in dem Temperaturbereich von ca. 900°C bis 1100°C als wesentlich wirkender Inhibitor fein verteilte MnS-Teilchen eingestellt werden und die Elektrobleche in der Regel nur eine magnetische Induktion B8 von weniger als etwa 1,88 T besitzen.In contrast to the method according to the invention, it is characteristic in the previous conventional production of RGO electrical sheets (for example according to DE-A1 41 16 240) that in this case the slabs only have a max. Contain 0.005% Al, which are heated before the hot rolling at a temperature in the order of approx. 1400 ° C, by the hot rolling and, if necessary, by subsequent heat treatment of the rolled strips in the temperature range from approx. 900 ° C to 1100 ° C finely distributed MnS particles are set as an essential inhibitor and the electrical sheets generally have only a magnetic induction B 8 of less than about 1.88 T.

Bei den bisherigen konventionellen Verfahren zur Herstellung von HGO-Elektroblechen (z.B. nach der DE-C2 29 09 500) ist kennzeichnend, daß die Brammen ca. 0,010 bis zu 0,065 % Al enthalten, die Brammen vor dem Warmwalzen ebenfalls bei einer Temperatur in der Größenordnung von ca. 1400°C durcherwärmt werden, durch das Warmwalzen und durch die sich daran anschließende Warmbandglühung wesentlicher Inhibitor fein verteilte AlN-Teilchen sind und solche Elektrobleche vorzugsweise eine magnetische Induktion B8 von größer 1,88 T besitzen.In the previous conventional processes for the production of HGO electrical sheets (for example according to DE-C2 29 09 500) it is characteristic that the slabs contain approx. 0.010 to 0.065% Al, the slabs also before the hot rolling at a temperature of the order of magnitude of about 1400 ° C, are hot inhibitors by the hot rolling and subsequent hot strip annealing are finely divided AlN particles and such electrical sheets preferably have a magnetic induction B 8 greater than 1.88 T.

Wie anhand der nachfolgenden Ausführungsbeispielen gezeigt und das erfindungsgemäße Verfahren im einzelnen erläutert wird, können nach dem erfindungsgemäßen Verfahren nunmehr kornorientierte Elektrobleche hergestellt werden mit der gleichen magnetischen Induktion B8 in Tesla (T), wie sie RGO- und auch HGO-Elektrobleche besitzen, jedoch mit verbesserten Werten für den Ummagnetisierungsverlust P1,7/50 in Watt pro kg (W/kg).As shown with reference to the following exemplary embodiments and the method according to the invention is explained in detail, grain-oriented electrical sheets can now be produced using the method according to the invention with the same magnetic induction B 8 in Tesla (T) as RGO and also HGO electrical sheets have with improved values for the magnetic loss P 1.7 / 50 in watts per kg (W / kg).

Nach dem erfindungsgemäßen Verfahren werden zunächst mit Hilfe des bekannten Stranggieß-Verfahrens Brammen mit einer Ausgangsdicke in dem Bereich von 150 bis 300 mm, vorzugsweise in dem Bereich von 200 bis 250 mm, erzeugt. Alternativ können die Brammen auch sogenannte Dünnbrammen mit einer Ausgangsdicke in dem Bereich von ca. 30 bis 70 mm sein. In vorteilhafter Weise kann in diesen Fällen bei der Herstellung des Warmbandes nach dem Verfahrensschritt (3) auf das Vorwalzen auf eine Zwischendicke verzichtet werden. Ferner können kornorientierte Elektrobleche nach dem erfindungsgemäßen Verfahren auch aus Brammen oder Bändern mit einer noch geringeren Ausgangsdicke hergestellt werden, wenn diese Brammen oder Bänder zuvor mit Hilfe des Bandgießens erzeugt wurden.According to the method of the invention are first of all with the help of the known continuous casting process slabs with an initial thickness in the range of 150 to 300 mm, preferably in the Range from 200 to 250 mm. Alternatively, the Slabs also known as thin slabs with an initial thickness in be in the range of approximately 30 to 70 mm. Advantageously can be used in these cases during the production of the hot strip the process step (3) on the roughing to an intermediate thickness to be dispensed with. Grain-oriented electrical sheets can also be used by the process according to the invention also from slabs or tapes with an even smaller starting thickness if using these slabs or tapes beforehand of the strip casting were generated.

Die Brammen, Dünnbrammen oder Bänder, im folgenden kurz Brammen genannt und so definiert, enthalten den im Oberbegriff und im kennzeichnenden Teil des Patentanspruches 1 angegebenen Gehalt an Kohlenstoff, Silizium, Mangan, Stickstoff und Kupfer sowie im Vergleich zum Stand der Technik (gemäß der EP-B1 0 219 611) den erfindungsgemäß angehobenen Schwefelgehalt in dem Bereich von mehr als 0,010, vorzugsweise größer 0,015 %, bis zu 0,050 % und den gezielt in den unteren bekannten Bereich abgesenkten Aluminiumgehalt in dem Bereich von 0,010 bis zu 0,030 %, max. bis zu 0,035 %, Rest Fe einschließlich Verunreinigungen. Vorzugsweise werden die in dem Patentanspruch 2 angegebenen Gehalte an Aluminium und Schwefel eingestellt. Auch der Gehalt der übrigen Legierungsbestandteile liegt vorzugsweise für jedes Legierungselement einzeln oder in Kombination innerhalb der in dem Patentanspruch 2 angegebenen Bereiche.The slabs, thin slabs or strips, hereinafter briefly slabs named and so defined, contain the in the preamble and in characterizing part of claim 1 specified content of carbon, silicon, manganese, nitrogen and copper as well compared to the prior art (according to EP-B1 0 219 611) the sulfur content according to the invention in the range from more than 0.010, preferably greater than 0.015%, up to 0.050% and the one specifically lowered into the lower known area Aluminum content in the range from 0.010 to 0.030%, max. up to 0.035%, balance Fe including impurities. Preferably the contents specified in claim 2 adjusted to aluminum and sulfur. The salary too the remaining alloy components are preferably for each Alloy element individually or in combination within the areas specified in claim 2.

In vorteilhafter Weise werden nach erfolgtem erfindungsgemäßen Verfahrensschritt (3) nur in geringem Umfang Risse an den Warmbandkanten festgestellt und damit gute Warmbandkanten und dementsprechend ein hohes Ausbringen erzielt, nach durchgeführtem Verfahrensschritt (4) eine feinere Verteilung der als wesentlicher Inhibitor wirkenden Kupfer-Sulfid-Teilchen gefunden und insgesamt nach Beendigung des Verfahrens gemäß Oberbegriff kornorientierte Elektrobleche mit hohen Werten für die magnetische Induktion B8 dann erzeugt, wenn der Gehalt der Brammen an Mangan, Kupfer und Schwefel so eingestellt wird, daß die Abstimmungsregel gemäß Patentanspruch 3 erfüllt ist und insbesondere zusätzlich der Mangan- und Schwefel-Gehalt in den beiden in dem Patentanspruch 4 angegebenen Bereichen liegt.Advantageously, after process step (3) according to the invention, cracks are only detected to a small extent on the hot strip edges and thus good hot strip edges and accordingly a high output are achieved, after process step (4) a finer distribution of the copper sulfide particles acting as an essential inhibitor found and after the end of the process according to the preamble grain-oriented electrical sheets with high values for the magnetic induction B 8 generated when the slab content of manganese, copper and sulfur is set so that the voting rule according to claim 3 is met and in particular additionally Manganese and sulfur content is in the two ranges specified in claim 4.

Nach den Patentansprüchen 1 oder 5 kann der Zusammensetzung noch Zinn bis zu 0,15 %, vorzugsweise jedoch nur 0,02-0,06 %, zugegeben werden. Die magnetischen Eigenschaften werden hierdurch nicht weiter verbessert.According to claims 1 or 5, the composition tin up to 0.15%, but preferably only 0.02-0.06%, be added. This will make the magnetic properties not further improved.

Im Anschluß an die Erzeugung der Brammen mit der in dem Patentanspruch 1, vorzugsweise mit der in den Patentansprüchen 2, 3 und 4, angegebenen Legierungszusammensetzung werden diese auf eine Temperatur erwärmt und bei dieser Temperatur durcherwärmt, die in dem mit dem erfindungsgemäßen Verfahrensschritt (2) angegebenen Temperaturbereich liegt. Dabei muß diese von dem vorgegebenen Mangan-, Schwefel- und Silizium-Gehalt abhängige Temperatur in jedem Fall kleiner sein als die zugehörige Lösungstemperatur T1 für Mangansulfide und gleichzeitig deutlich oberhalb der zugehörigen Lösungstemperatur T2 für Kupfersulfide liegen. Dieser Temperaturbereich ist aus Figur 3 ersichtlich, die eine gemeinsame Darstellung der Löslichkeitskurven gemäß Figur 1 und gemäß Figur 2 zeigt.Following the production of the slabs with the alloy composition specified in patent claim 1, preferably with the alloy claims specified in patent claims 2, 3 and 4, they are heated to a temperature and heated through at this temperature, which in the process step (2) according to the invention specified temperature range. This temperature, which is dependent on the predetermined manganese, sulfur and silicon content, must in any case be lower than the associated solution temperature T 1 for manganese sulfides and at the same time be significantly above the associated solution temperature T 2 for copper sulfides. This temperature range can be seen from FIG. 3, which shows a common representation of the solubility curves according to FIG. 1 and according to FIG. 2.

Figur 1 zeigt die Löslichkeitskurve T1=f (Mn, S, 3,0 % - 3,2 % Si) für Mangansulfid, Figur 2 die Löslichkeitskurve T2=f (Cu, S, 3,0 % - 3,2 % Si) für Kupfersulfid. Die Figuren 1, 2 und 3 verdeutlichen das Lösungsverhalten für kornorientierte Elektrobleche mit üblichen Si-Gehalten. Die berücksichtigten Gehalte entsprechen den in Tabelle 1, 2 und 3 dargestellten Ausführungsbeispielen.Figure 1 shows the solubility curve T 1 = f (Mn, S, 3.0% - 3.2% Si) for manganese sulfide, Figure 2 shows the solubility curve T 2 = f (Cu, S, 3.0% - 3.2% Si) for copper sulfide. Figures 1, 2 and 3 illustrate the solution behavior for grain-oriented electrical sheets with usual Si contents. The contents taken into account correspond to the exemplary embodiments shown in Tables 1, 2 and 3.

Die Durchführung des Verfahrensschrittes (2) bewirkt, daß bei der Durcherwärmung der Brammen vor dem Warmwalzen Mangansulfide praktisch nicht in Lösung gebracht werden. Da die entsprechenden Löslichkeitskurven für Aluminiumnitride den Löslichkeitskurven für Mangansulfide ähnlich bzw. vergleichbar sind, wird bei der erfindungsgemäßen Durcherwärmung der Brammen auch bereits der überwiegende Anteil an Aluminiumnitriden ausgeschieden. Nach Beendigung dieses Verfahrensschrittes befinden sich praktisch nur Kupfersulfide fast vollständig in Lösung.Carrying out process step (2) causes that heating of the slabs before hot rolling manganese sulfides practically cannot be brought into solution. Because the corresponding Solubility curves for aluminum nitride the solubility curves are similar or comparable for manganese sulfides already in the heating of the slabs according to the invention the majority of aluminum nitrides excreted. After completing this step practically only copper sulfides are almost completely in solution.

Nach erfolgter Lösungsglühung der Brammen werden diese nach dem erfindungsgemäßen Verfahrensschritt (3) ggf. zunächst in Abhängigkeit von der Ausgangsdicke der Brammen in 3 bis 7 Stichen vorgewalzt und anschließend in 5 bis 9 Stichen auf die Warmband-Enddicke in dem Bereich von 1,5 bis 5 mm, max. bis 7 mm fertiggewalzt. Dabei erfolgt das Vorwalzen von Brammen mit einer Ausgangsdicke in dem Bereich von 150 bis 300 mm, vorzugsweise in dem Bereich von 200 bis 250 mm, bis auf eine Vorband-Dicke in dem Bereich von ca. 30 bis 60 mm. Insgesamt richtet sich dabei die Anzahl der Stiche während des Vorwalzens und während des Fertigwalzens nach der Ausgangsdicke der Brammen und nach der gewünschten Warmband-Enddicke.After solution annealing of the slabs, these are after the Method step (3) according to the invention may be dependent first from the initial thickness of the slabs in 3 to 7 stitches pre-rolled and then in 5 to 9 passes to the final hot strip thickness in the range from 1.5 to 5 mm, max. up to 7 mm finish rolled. The slabs are pre-rolled with a Initial thickness in the range of 150 to 300 mm, preferably in the range from 200 to 250 mm, except for a pre-strip thickness in the range of approx. 30 to 60 mm. Overall, the number of Stitches during roughing and finish rolling according to the starting thickness of the slabs and according to the desired one Final hot strip thickness.

Wesentliches Merkmal des Verfahrensschrittes (3) ist jedoch, daß die Bänder mit einer möglichst niedrigen Endwalztemperatur in dem Bereich von 880°C bis 1000°C, vorzugsweise in dem Bereich von 900°C bis 980°C, fertiggewalzt werden. Dabei wird die untere Grenze dadurch bestimmt, daß noch eine problemlose Verformung bzw. ein Walzen der Bänder ohne auftretende Schwierigkeiten, wie z.B. Bandunebenheiten und Bandprofilabweichungen, möglich sein muß. In Verbindung mit dem Verfahrensschritt (2) wird nach Beendigung des Verfahrensschrittes (3) gefunden, daß in dem Warmband grobe MnS-Teilchen und sehr viele grobe AlN-Teilchen mit einem mittleren Durchmesser von mehr als 100 nm ausgeschieden vorliegen. Nach der Beendigung des erfindungsgemäßen Warmwalzens liegen mehr als 60 % des Gesamtstickstoffgehaltes an Aluminium gebunden in Form von AlN vor. Ein Maß für die Menge Stickstoff, die an Aluminium gebunden vorliegt, ist der N-Beeghley-Wert. Seine Bestimmung erfolgt nach einem chemischen Verfahren, das in "Analytical Chemistry, Volume 21, No. 12, Dezember 1949" beschrieben ist. Demgegenüber liegen bei den Verfahren zur Herstellung von HGO-Elektroblechen nach der Lösungsglühung der Brammen und nach Beendigung des Warmwalzens nur sehr wenige MnS-Teilchen und praktisch keine AlN-Teilchen mit dieser Teilchengröße (d.h. kleiner 100 nm) vor.The essential feature of process step (3) is, however, that the strips with the lowest possible final rolling temperature in the range of 880 ° C to 1000 ° C, preferably in the range from 900 ° C to 980 ° C. The lower limit determined by the fact that there is still a problem-free deformation or rolling the strips without any difficulties, such as. Strip unevenness and strip profile deviations, must be possible. In connection with the process step (2) is found after process step (3) has ended, that coarse MnS particles in the hot strip and very many coarse AlN particles with an average diameter of more than 100 nm are present. After the completion of the invention Hot rolling is more than 60% of the total nitrogen content bound to aluminum in the form of AlN. A Measure of the amount of nitrogen present in aluminum is the N-Beeghley value. Its determination follows a chemical process described in "Analytical Chemistry, Volume 21, No. 12, December 1949 ". In contrast lie in the processes for the production of HGO electrical sheets after the solution annealing of the slabs and after completion of the Hot rolling only very few MnS particles and practically none AlN particles with this particle size (i.e. smaller than 100 nm) in front.

Im Anschluß daran erfolgt die Wärmebehandlung der warmgewalzten Bänder nach dem erfindungsgemäßen Verfahrensschritt (4) in dem Temperaturbereich von 880°C bis 1150°C, vorzugsweise in nur einer Stufe in dem Temperaturbereich vom 950°C bis 1100°C. Sie kann jedoch auch mehrstufig erfolgen. Durch diese Wärmebehandlung werden die in den nachfolgenden Verfahrensschritten als Inhibitor wirkenden Teilchen mit einem mittleren Durchmesser von weniger als 100 nm, vorzugsweise kleiner 50 nm, ausgeschieden. So werden bei dem erfindungsgemäßen Verfahren nach der Warmbandglühung eine große Anzahl feiner Kupfer-Sulfid-Teilchen dieser Teilchengröße und im Vergleich dazu nur eine sehr geringe Anzahl feiner AlN-Teilchen gefunden. Demgegenüber liegen bei den Verfahren zur Herstellung von HGO-Elektroblechen praktisch ausschließlich feine AlN-Teilchen dieser Größe vor.This is followed by the heat treatment of the hot-rolled Tapes according to process step (4) according to the invention in the Temperature range from 880 ° C to 1150 ° C, preferably in only one Level in the temperature range from 950 ° C to 1100 ° C. she can also be done in several stages. Through this heat treatment are used in the subsequent process steps particles with an average diameter acting as an inhibitor of less than 100 nm, preferably less than 50 nm, excreted. So in the method according to the invention hot strip annealing a large number of fine copper sulfide particles this particle size and only one in comparison very small number of fine AlN particles found. In contrast lie in the processes for the production of HGO electrical sheets practically exclusively fine AlN particles of this size.

Tabelle 4 verdeutlicht, wie durch das erfindungsgemäße Verfahren die Art und Größe der Ausscheidungen, und damit ihre Wirksamkeit als Inhibitor, beeinflußt werden. Es zeigt ferner die Unterschiede gegenüber den vorliegenden Ausscheidungen, die durch Verfahren gemäß dem Stand der Technik (HGO, RGO) erzielt werden.Table 4 illustrates how the invention Process the type and size of the excretions, and thus their Effectiveness as an inhibitor. It also shows the differences from the present excretions, the achieved by methods according to the state of the art (HGO, RGO) will.

Wie die in Tabelle 3 angegebenen Vergleichsbeispiele 14 und 15 zeigen, sind wesentliche Merkmale des erfindungsgemäßen Verfahrens, daß die Brammen notwendigerweise einen Schwefelgehalt größer 0,010 %, vorzugsweise größer 0,015 %, enthalten müssen und daß in jedem Fall zur Ausscheidung der feinen Kupfer-Sulfid-Teilchen die Warmbandglühung gemäß Verfahrensschritt (4) durchzuführen ist. Entfällt die Warmbandglühung (4), so liegen keine als Inhibitor in den nachfolgenden Verfahrensschritten wirkenden Teilchen kleiner 100 nm, vorzugsweise kleiner 50 nm, in genügend großer Anzahl vor, und zwar wegen des vorzeitigen Ausscheidens von groben MnS- und AlN-Teilchen aufgrund der Verfahrensschritte (2) und (3).Like Comparative Examples 14 and 15 given in Table 3 show are essential features of the method according to the invention, that the slabs necessarily have a sulfur content must contain greater than 0.010%, preferably greater than 0.015% and that in any case for the precipitation of the fine copper sulfide particles hot strip annealing according to process step (4) is to be carried out. If hot strip annealing (4) is not used, lie there none as an inhibitor in the subsequent process steps acting particles smaller than 100 nm, preferably smaller than 50 nm, in sufficient numbers because of the premature Elimination of coarse MnS and AlN particles due to the process steps (2) and (3).

Nach durchgeführter Warmbandglühung (4) erfolgt das Kaltwalzen der Bänder vorzugsweise einstufig bis auf die Fertigbanddicke in dem Bereich von 0,1 bis 0,5 mm. In Abhängigkeit von der WarmbandEnddicke kann das Kaltwalzen gemäß Patentanspruch 6 auch in zwei Stufen erfolgen, wobei gemäß Patentanspruch 7 vor der ersten Kaltwalzstufe vorzugsweise eine Vorglühung durchgeführt wird. Diese trägt in vorteilhafter Weise zur Stabilisierung der Sekundärrekristallisation in der nachfolgenden Hochtemperaturglühung bei.After hot strip annealing (4) has been carried out, cold rolling takes place the tapes preferably in one step to the finished tape thickness in the range of 0.1 to 0.5 mm. Depending on the The final hot strip thickness can be cold rolled according to claim 6 also take place in two stages, according to claim 7 before the first cold rolling stage is preferably preheated becomes. This contributes to stabilization in an advantageous manner secondary recrystallization in the subsequent high-temperature annealing at.

Im Anschluß an das Kaltwalzen bis auf die gewünschte Enddicke erfolgt das an sich bekannte rekristallisierende und entkohlende Glühen der Bänder bei einer Temperatur in dem Bereich von 750°C bis 900°C, vorzugsweise bei einer Temperatur in dem Bereich von 820°C bis 880°C, in einer feuchten H2 und N2 enthaltenden Atmosphäre. Daran anschließend wird ein primär MgO enthaltender Glühseperator aufgetragen. Die Bänder werden anschließend in bekannter Weise in einer Langzeit-Haubenglühung mit einer langsamen Aufheizung von 10 bis 100 K/h, vorzugsweise 15 bis 25 K/h, auf mindestens 1150°C bei dieser Temperatur in einer aus H2 und N2 bestehenden Atmosphäre geglüht und nach einem Halten für 0,5 bis 30 h langsam wieder abgekühlt. Zum Abschluß erfolgt die ebenfalls bekannte Isolationsbeschichtung mit der dazugehörigen Schlußglühung.Following cold rolling to the desired final thickness, the recrystallizing and decarburizing annealing of the strips, which is known per se, is carried out at a temperature in the range from 750 ° C. to 900 ° C., preferably at a temperature in the range from 820 ° C. to 880 ° C, in a humid atmosphere containing H 2 and N 2 . A glow separator containing primarily MgO is then applied. The strips are then in a known manner in a long-term hood annealing with a slow heating of 10 to 100 K / h, preferably 15 to 25 K / h, to at least 1150 ° C at this temperature in an atmosphere consisting of H 2 and N 2 annealed and slowly cooled again after holding for 0.5 to 30 h. Finally, the insulation coating, which is also known, is carried out with the associated final annealing.

Anhand von acht Ausführungsbeispielen zeigt Tabelle 1 die Ergebnisse bei Anwendung des erfindungsgemäßen Verfahrens nach Patentanspruch 1 auf Brammen mit einer Ausgangsdicke von 215 mm. In Tabelle 2 sind weitere Ergebnisse zusammengestellt, die nach dem erfindungsgemäßen Verfahren gemäß Patentanspruch 1 in Kombination mit den Verfahrensschritten gemäß den Unteransprüchen 6 und 7 erzielt werden. Das Kaltwalzen erfolgte in diesen Fällen in zwei Stufen ohne und auch mit der Vorglühung vor der ersten Kaltwalzstufe gemäß Patentanspruch 7.Table 1 shows the results using eight exemplary embodiments when using the method according to the invention Claim 1 on slabs with an initial thickness of 215 mm. Table 2 shows further results, that according to the inventive method according to claim 1 in combination with the procedural steps according to the subclaims 6 and 7 can be achieved. The cold rolling took place in these cases in two stages without and also with the preheating before the first cold rolling stage according to claim 7.

Wie sich aus den Tabellen 1 und 2 ergibt, können kornorientierte Elektrobleche hergestellt werden, die eine magnetische Induktion B8 besitzen, wie sie auch kornorientierte Elektrobleche sowohl der Güte RGO als auch der Güte HGO aufweisen. Mit Hilfe des erfindungsgemäßen Verfahrens werden diese Güten nunmehr jedoch nur durch die Anwendung eines einzigen Verfahrens mit den in dem Patentanspruch 1 angegebenen Verfahrensschritten erzielt. Ferner werden neben den Vorteilen der abgesenkten Temperatur für die Lösungsglühung der Brammen in den entsprechenden Öfen in vorteilhafter Weise wesentlich günstigere Werte für die zugehörigen Ummagnetisierungsverluste erreicht. Dies verdeutlicht Figur 4, in der für kornorientierte Elektrobleche mit einer Fertigbanddicke von 0,30 mm die in Tabelle 1 und 2 angegebenen Werte für die magnetische Induktion und den Ummagnetisierungsverlust grafisch als Kurve TGO (Thyssen Grain Oriented) dargestellt sind. Ferner sind im Vergleich dazu der Figur 4 die entsprechenden und typischen Wertepaare für kornorientierte Elektrobleche der Güten RGO und HGO zu entnehmen, die bisher nur in bekannter Weise mit Hilfe von zwei getrennten unterschiedlichen Verfahren hergestellt werden können.

Figure 00150001
Figure 00160001
Figure 00170001
Figure 00180001
As can be seen from Tables 1 and 2, grain-oriented electrical sheets can be produced which have a magnetic induction B 8 , as they also have grain-oriented electrical sheets of both the RGO grade and the HGO grade. With the aid of the method according to the invention, however, these grades are now only achieved by using a single method with the method steps specified in claim 1. Furthermore, in addition to the advantages of the reduced temperature for the solution annealing of the slabs in the corresponding furnaces, values which are substantially more favorable for the associated magnetic reversal losses are advantageously achieved. This is illustrated in FIG. 4, in which, for grain-oriented electrical sheets with a finished strip thickness of 0.30 mm, the values for the magnetic induction and the loss of magnetic reversal indicated in Tables 1 and 2 are shown graphically as a curve TGO (Thyssen Grain Oriented). Furthermore, in comparison to this, FIG. 4 shows the corresponding and typical value pairs for grain-oriented electrical sheets of the RGO and HGO grades, which until now could only be produced in a known manner using two separate, different processes.
Figure 00150001
Figure 00160001
Figure 00170001
Figure 00180001

Claims (19)

  1. A process for the production of grain oriented magnetic steel sheets having a finished strip thickness in the range of 0.1 mm to 0.5 mm, wherein slabs produced by continuous casting and containing more than 0.005 % to 0.10 % C, 2.5 to 6.5 % Si and 0.03 to 0.15 % Mn are first through-heated in one or two stages and then hot roughed and finish rolled to a hot strip final thickness, whereafter the strips, hot rolled to the final thickness, are annealed and rapidly cooled and cold rolled in one or more cold rolling stages for the finished strip thickness, the cold rolled strips being then subjected to a recrystallizing annealing in a wet atmosphere containing H2 and N2 with simultaneous decarburization, the application of a separating agent mainly containing MgO to the cold strip surface on both sides, a high temperature annealing and lastly a final annealing with an insulating coating, wherein
    (1) the slabs also contain
       more than
    0.010 to 0.050 % S,
    0.010 to max. 0.035 % Al,
    0.0045 to 0.0120 % N,
    0.020 to 0.300 % Cu,
    optionally up to 0.15 % Sn
    residue Fe, including impurities,
    (2) prior to hot rolling the slabs produced are through-heated at a temperature which is lower than the solubility temperature T1 of manganese sulphide, in dependence on the particular Si content, and higher than the solubility temperature T2 of copper sulphides, in dependence on the particular Si content,
    (3) the through-heated slabs are then first hot roughed to an intermediate thickness and subsequently or immediately thereafter hot finish rolled with a charge temperature of at least 960 °C and final rolling temperature in the range of 880 °C to 1000 °C to a hot strip final thickness in the range of 1.5 to 7 mm, for the precipitation of nitrogen in a quantity of at least 60 % of the total nitrogen content in the Form of coarse AlN particles,
    (4) the hot rolled strips are then annealed for 100 to 600 sec at a temperature in the range of 880 °C to 1150 °C, whereafter they are cooled at a cooling rate higher than 15 K/sec, for the precipitation of nitrogen up to the maximum possible quantity of the total nitrogen content in the form of coarse and fine AlN particles and for the precipitation of fine copper sulphide particles.
  2. A process according to claim 1, characterised in that the slabs contain
    3.0 to 3.3 % Si,
    0.040 to 0.070 % C,
    0.050 to 0.150 % Mn,
    0.020 to 0.035 % S,
    0.015 to 0.025 % Al,
    0.0070 to 0.0090 % N,
    0.020 to 0.200 % Cu,
    residue Fe, including impurities.
  3. A process according to claims 1 or 2, characterised in that the Mn, Cu and S contents of the slabs are so adjusted that the product of the Mn and Cu content divided by the S content is in the range of 0.1 to 0.4: (Mn x Cu) / S = 0.1 to 0.4.
  4. A process according to one of claims 1 to 3,
    characterised in that the slabs contain
    0.070 to 0.100 % Mn and
    0.020 to 0.025 % S.
  5. A process according to claim 1, characterised in that the slabs contain 0.02 % to 0.06 % Sn.
  6. A process according to one of claims 1 to 5,
    characterised in that the charge temperature in hot rolling is higher than 1000 °C.
  7. A process according to one of claims 1 to 6,
    characterised in that the final rolling temperature is in the range of 900 °C to 980 °C.
  8. A process according to one of claims 1 to 7,
    characterised in that the hot rolled strip is annealed in the temperature range of 950 ° C to 1100 °C.
  9. A process according to one of claims 1 to 8,
    characterised in that following annealing, the hot rolled strip is cooled at a cooling rate higher than 25 K/sec.
  10. A process according to one of claims 1 to 9,
    characterised in that the strips rolled to the hot strip final thickness are rapidly cooled to a coiling temperature of lower than 700 °C.
  11. A process according to one of claims 1 to 10,
    characterised in that prior to process step (4) the hot rolled strips are first roughed in the first cold rolling stage to an intermediate thickness and following process step (4) the annealed strips are rolled in the second cold rolling stage with a degree of reduction of at least 65 % to the finished coil thickness.
  12. A process according to claim 11, characterised in that the annealed strips are rolled in the second cold rolling stage with a degree of reduction of at least 75 %.
  13. A process according to claims 11 or 12, characterised in that prior to the first advanced cold rolling stage the strips rolled to the hot strip final thickness are annealed at a temperature in the range of 800 °C to 1000 °C.
  14. A process according to one of claims 1 to 13,
    characterised in that the final cold rolling stage the strips are held for at least one pass at a temperature in the range of 100 °C to 300 °C.
  15. A grain oriented magnetic steel sheet produced by a process as set forth in one of claims 1 to 14,
    characterised in that following the annealing and cooling (4) of the hot rolled strip, more than 60 % of the copper sulphide particles are present as an inhibitor.
  16. A grain oriented magnetic steel sheet according to claim 15, characterised in that more than 80 % of copper sulphide particles are present.
  17. A grain oriented magnetic steel sheet according to claims 15 or 16, characterised in that a proportion of the copper sulphide particles are present in the form of copper-iron sulphide particles of the copper-manganese sulphide particles.
  18. A grain oriented magnetic steel sheet according to one of claims 15 to 17, characterised in that the copper sulphide particles present have an average diameter smaller than 100 nm.
  19. A grain oriented magnetic steel sheet according to claim 19, characterised in that the copper sulphide particles present have a average diameter smaller than 50 nm.
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