EP2759614B1 - Procédé destiné à générer un produit plat en acier avec une structure cristalline fine, partiellement amorphe ou amorphe et produit plat en acier conçu de la sorte - Google Patents

Procédé destiné à générer un produit plat en acier avec une structure cristalline fine, partiellement amorphe ou amorphe et produit plat en acier conçu de la sorte Download PDF

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Publication number
EP2759614B1
EP2759614B1 EP13152793.9A EP13152793A EP2759614B1 EP 2759614 B1 EP2759614 B1 EP 2759614B1 EP 13152793 A EP13152793 A EP 13152793A EP 2759614 B1 EP2759614 B1 EP 2759614B1
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EP
European Patent Office
Prior art keywords
casting
amorphous
strip
cooled
cast strip
Prior art date
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EP13152793.9A
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German (de)
English (en)
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EP2759614A1 (fr
Inventor
Dorothée DORNER
Christian Höckling
Harald Hofmann
Matthias Schirmer
Markus DAAMEN
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ThyssenKrupp Steel Europe AG
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ThyssenKrupp Steel Europe AG
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Priority to EP13152793.9A priority Critical patent/EP2759614B1/fr
Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Priority to KR1020157022868A priority patent/KR102203018B1/ko
Priority to EP14701377.5A priority patent/EP2948572A1/fr
Priority to JP2015554158A priority patent/JP6457951B2/ja
Priority to PCT/EP2014/051416 priority patent/WO2014114756A1/fr
Priority to US14/763,249 priority patent/US10730105B2/en
Priority to CN201480018468.1A priority patent/CN105143491B/zh
Priority to BR112015017627-5A priority patent/BR112015017627B1/pt
Publication of EP2759614A1 publication Critical patent/EP2759614A1/fr
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Publication of EP2759614B1 publication Critical patent/EP2759614B1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/06—Special casting characterised by the nature of the product by its physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • 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
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/005—Heat treatment of ferrous alloys containing Mn
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/003—Making ferrous alloys making amorphous alloys
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • 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
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/03—Amorphous or microcrystalline structure

Definitions

  • the invention relates to a method for producing a flat steel product having an amorphous, partially amorphous or fine-crystalline microstructure, the fine-crystalline microstructure having particle sizes in the range from 10 to 10,000 nm, and a flat steel product having an amorphous, partially amorphous or fine-crystalline microstructure of this type.
  • a molten steel is poured into a cast strip in a casting device and cooled down at an accelerated rate.
  • a steel melt containing at least two further elements from the group "Si, B, C and P" in addition to iron and production-dependent unavoidable impurities in a casting device the casting region at least one of its longitudinal sides is formed by a moving in the casting during the casting and cooled wall, cast into a cast strip.
  • the region of the casting device in which the cast strip is formed is referred to as the "casting region”.
  • two-roller casting device also known in technical terminology as a “twin-roller casting machine”.
  • two casting rolls or casting rolls aligned axially parallel to one another rotate in the casting operation and limit a casting gap defining the casting region in the region of their closest separation.
  • the casting rolls are strongly cooled, so that the melt meeting them solidifies to a shell.
  • the direction of rotation of the casting rolls is chosen so that the melt and with it the shells formed from it on the casting rolls are transported into the casting gap.
  • the trays entering the casting gap are compressed to the cast strip under the effect of sufficient banding force.
  • Another pouring device for strip casting is based on the principle of "belt casting” technology.
  • liquid steel is introduced via a feed system poured round casting tape.
  • the direction of the tape is chosen so that the melt is conveyed away from the feed system.
  • a second casting belt can be arranged, which rotates in opposite directions to the first casting belt.
  • At least one casting belt limits the mold, by which the cast strip is formed, even in the above-mentioned methods.
  • the respective casting belt is intensively cooled, so that the melt coming into contact with the casting belt in question is solidified at the turning point of the casting belt facing away from the supply system to form a belt which can be removed from the casting belt.
  • the cast strip emerging from the respective casting device is drawn off, cooled and fed to further processing.
  • This further processing may include a heat treatment and a hot rolling.
  • the particular advantage of strip casting here is that the steps following the strip casting can be completed in a continuous, uninterrupted sequence.
  • steels which are suitable for the production of steel strips with an amorphous, partially amorphous or fine-crystalline structure can be alloys based on iron and one or more elements from the group "B, C, Si, P, Ga” In addition to these elements in addition contents of Cr, Mo, W, Ta, V, Nb, Mn, Cu, Al, Co and rare earths may be present.
  • Alloys so formed are said to be cast strip tapes having a fine-grained, nanocrystalline, or near-nanocrystalline texture in which more than 90% of the grains are 5 ⁇ -1 ⁇ m in size, the melting point of the steel from which the cast iron is cast Consist of tapes in the range of 800-1500 ° C, the critical cooling rate of the steel is less than 10 5 K / s and the cast tapes contain ⁇ -Fe and / or ⁇ -Fe phases.
  • the object of the invention was to provide practical methods for the production of flat steel products which have an amorphous, partially amorphous or fine-grained structure.
  • a flat steel product should be specified, which can be produced inexpensively in a practical way.
  • a flat steel product is understood a cast or rolled steel strip or sheet and derived therefrom blanks, blanks or the like.
  • a first object solving this object according to the invention is specified in claim 1.
  • the solution according to the invention of the above-stated object is that such a flat steel product has the features mentioned in claim 14.
  • the invention mentions operating conditions with which, for practice, sufficient reproducibility from a steel containing at least two further elements from the group "Si, B, Cu, P" in addition to iron and unavoidable impurities, cast strips with amorphous, partially amorphous or can produce fine-crystalline structure.
  • those alloys are preferred in which, in addition to the respectively unavoidable production reasons but ineffective constituents with respect to the properties of the steel flat products produced according to the invention, besides iron, only two further elements of the group "Si, B, C, P" are present in the amounts prescribed according to the invention.
  • such alloys in addition to Fe and unavoidable impurities, only the alloy element pairs Si and B, Si and C, Si and P, B and C, B and P or C and P are present in the steel.
  • Such composite steel alloys are particularly suitable for amorphous or teilamorphe solidification.
  • said alloy pairs can be supplemented by one or two other alloying elements of the group "Si, B, C, P".
  • the alloying elements of the group "Si, B, C, P" which are not within the specifications according to the invention, although present in measurable levels, where they may have an effect, but in which they at most subordinate contribute to the formation of the invention sought after structure. That is, according to the invention, in each case two elements from the group "Si, B, C, P" must be present in the levels specified in the invention in order to produce inventive flat steel product, which does not preclude the respective other elements of the group "Si, B , C, P "are present in contents which are outside the specifications according to the invention.
  • a presence of an alloying element of the group "Si, B, C, P" contained outside the specifications according to the invention is particularly possible if its content is below the lower limit prescribed according to the invention for the content of the relevant element.
  • the widest composition of a steel according to the invention thus comprises as obligatory constituents at least two of the elements boron, silicon, carbon and phosphorus as well as the remainder iron and unavoidable impurities. These elements prove to be particularly advantageous because they can be procured at relatively low cost.
  • the production method according to the invention enables a reproducible production of a steel product with an amorphous, partially amorphous or fine-crystalline structure.
  • a flat steel product produced according to the invention has a finely crystalline microstructure with particle sizes in the range from 10 to 10,000 nm, it being possible in practice to regularly produce flat steel products whose grain sizes are limited to a maximum of 1000 nm.
  • the C in contents of up to 4.0% by weight promotes the amorphization of the material in flat steel products produced according to the invention.
  • the C content can be set to at least 1.0% by weight, especially 1.5% by weight.
  • settings of the contents of Si, B, C and P are obtained if, for the Si content% Si, 2.0% by weight ⁇ % Si ⁇ 6.0% by weight, in particular 3, 0% by weight ⁇ % Si 5.5% by weight, when the B content% B is 1.0% by weight ⁇ % B ⁇ 3.0% by weight, especially 1.5 wt .-% ⁇ % B ⁇ 3.0 wt .-%, if for the C content% C is 1.5 wt .-% ⁇ % C ⁇ 3.0 wt .-% or if for the P content% P is 2.0 wt% ⁇ % P ⁇ 6.0 wt%.
  • the ductility of the material can be increased, whereas the effect of Cr is mainly an improvement in corrosion resistance.
  • the addition of Al increases the corrosion resistance, but also has a supporting effect on the formation of an amorphous structure.
  • N can be considered as a possible substituent for C. Thus, the presence of N, as well as higher C contents, promotes the enhanced formation of an amorphous structure.
  • the molten steel can in each case optionally (in% by weight) at least 0.1% Cu, at least 0.5% Cr, at least 1.0% Al and at least 0.005% N included.
  • the steel alloy according to the invention can be produced with compulsory components which are conventional in the steel industry and which are comparatively inexpensive.
  • a steel strip having an amorphous, partially-amorphous or fine-crystalline structure of molten steel containing at least two of Si, B, C or P besides Fe and unavoidable impurities can be produced by a casting method.
  • a molten steel composition according to the invention is cast in a casting device into a cast strip whose casting region, in which the cast strip is formed, is formed on at least one of its longitudinal sides by a wall which moves and cools during the casting operation.
  • the wall which delimits the casting area and moves in the casting operation can be formed, in particular, by two counter-rotating casting rolls or a belt moving in the casting direction during the casting operation.
  • the molten steel is cooled by contact with the moving wall with at least 200 K / s.
  • the formation of the desired structure of the flat steel product can be ensured by performing the rapid cooling in practice to below the glass transition temperature T G of the respective steel. In this way, an amorphous or partially amorphous microstructure is first formed. On the basis of this microstructure, a finely crystalline microstructure can then be produced by means of a subsequent heat treatment above the crystallization temperature T x as a result of the resulting crystal nucleation and crystallization.
  • This approach has the advantage that the Feinkörnmaschine is very precisely adjustable, which is due to the Variety of forming nuclei sets a very homogeneous particle size distribution with very low fluctuation range.
  • the rapid cooling of the cast strip starting in the casting area after Exit from the casting area will continue.
  • the continued cooling sets in an advantageous manner immediately after the exit from the casting area, so that a largely continuous accelerated temperature decrease is ensured in the cast strip until the respective desired structural state is reached.
  • an additional cooling device can be provided, which is connected directly to the casting area of the casting device used for casting the cast strip.
  • the molten steel can be safely cooled to below the glass transition temperature T G with the cooling rate predetermined according to the invention in order to produce an amorphous or partially amorphous microstructure in the cast flat steel product.
  • the additional cooling device ensures that, in cases where there is only insufficient heat dissipation in the casting area of the casting device itself due to the contact with the moving and cooled wall of the casting area, the Cooling of the band is continued after the casting area so quickly that the microstructure state to be generated according to the invention is reliably achieved.
  • Another advantage of the additional, subsequent to the pouring device cooling is that can be controlled controlled with such cooling a specially adapted cooling curve. This may be useful if targeted cast tapes are to be obtained with a teilamorphen or fine crystalline structure as a result of the casting and cooling process.
  • the cooling can be carried out so that the glass transition temperature T G accelerates, but is not cooled in a sufficient for the expression of a fully amorphous structure speed.
  • the cast strip can be cooled accelerated according to the inventive specifications, but this cooling are stopped before reaching the glass transition temperature T G of each processed steel.
  • This way represents a first possibility to produce a predetermined, fine-crystalline structure in the resulting flat steel product.
  • the fine-crystalline structure is formed directly from the melt here, by allowing a controlled via the additional cooling crystallization.
  • Another way of producing a thin-crystalline steel flat product according to the invention is first to produce a strip with an amorphous or partially amorphous structure, which is then produced by an annealing process and a crystallization caused thereby is converted into a finely crystalline state.
  • the peculiarity of this procedure is that the crystallization takes place at a plurality of crystal nuclei and therefore the forming crystal grains are distributed very evenly in the material.
  • the crystallization temperature T x which is important for the development of the finely crystalline microstructure, is on average about 30-50 K above the glass transition temperature T G of the respective processed steel.
  • T G glass transition temperature
  • the inventively provided if necessary additional cooling device may be formed so that a cooling medium is added directly to the cast strip.
  • This cooling medium can be water, liquid nitrogen or another correspondingly effective cooling liquid.
  • cooling gases such as gaseous nitrogen, hydrogen, a gas mixture or water mist can also be applied. Suitable cooling devices for this purpose are known from the prior art ( KR2008 / 0057755A ).
  • the cooling rate critical for achieving an amorphous structure depends, inter alia, on the particular composition of the molten steel that is set. Thus, it may be appropriate to provide the cooling rates of more than 250 K / s, more than 450 K / s or even more than 800 K / s.
  • a particular aspect of finely crystalline steels of the type produced according to the invention is their ability to undergo structural superplasticity. Consequently, on the basis of flat steel products according to the invention, the most complex component geometries can be represented by grain boundary sliding processes at elevated temperatures (thermal activation).
  • a particularly process-reliable possibility of producing a flat steel product with a fine-crystalline structure provides that the cast strip emerging from the casting gap of the casting device and optionally additionally cooled thereafter has an amorphous or partially amorphous structure and that the cast strip produced in this way is then annealed at a minimum of the crystallization temperature Tx of the respective steel annealing temperature T anneal until the desired microstructure state is reached.
  • steel compositions are suitable for this purpose Annealing temperatures T annealing 500 - 1000 ° C.
  • annealing times of 2 s to 2 h are sufficient, depending on the specific concretely selected composition.
  • the belt speeds with which the cast strip emerges from the casting gap are typically in the range of 0.3-1.7 m / s in practice.
  • the strip thicknesses with which the cast and cooled strip according to the invention leaves the casting gap are typically in the range from 0.8 to 4.5 mm, in particular 0.8 to 3.0 mm.
  • the cast strip may be subjected to hot rolling in which the hot rolling start temperature should be 500-1000 ° C. Due to the hot rolling steps following the casting and cooling process in-line, on the one hand the desired final thickness of the strip and, on the other hand, the surface finish can be adjusted and the microstructure optimized, for example by closing still existing cavities in the cast state.
  • the hot rolling may also be hot rolled to the hot strip at a hot rolling start temperature in the range between the glass transition temperature T G and the crystallization temperature T x .
  • a two-roller casting is suitable, the mutually axially parallel to each other aligned axes rotating rollers each form a continuous casting in the casting continuously cooled longitudinal wall of the casting area, in which the band is formed.
  • the methods of the invention require only minor changes to existing methods and devices for the continuous production of close-to-scale flat steel products.
  • the invention will be explained in more detail with reference to a drawing illustrating an exemplary embodiment.
  • the single figure shows schematically a device for producing cast strip in a lateral view.
  • the plant 1 for producing a cast strip B comprises a casting device 2, which is constructed as a conventional two-roller casting device and accordingly two mutually aligned around axis-parallel to each other and at the same height axes X1, X2 rotating rollers 3,4.
  • the rollers 3, 4 are arranged with a thickness defining the thickness D of the cast strip B to be produced, and thus delimit on their longitudinal sides a casting area 5 in the form of a casting gap, in which the cast strip B is formed.
  • On its narrow sides of the casting area 5 in just as well known by not visible here side plates sealed, which are pressed against the end faces of the rollers 3,4.
  • the intensively cooled rollers 3, 4 rotate and in this way form longitudinal walls of a casting mold formed by the rollers 3, 4 and the side plates, which move continuously in the casting operation.
  • the direction of rotation of the rollers 3, 4 is directed in the direction of gravity R into the casting area 5, so that, as a result of the rotation, melt S is conveyed from the melt pool in the casting area 5, which is present in the space above the casting area 5 between the rollers 3, 4.
  • the melt S solidifies when it touches the peripheral surface of the rollers 3,4, due to the there taking place intense heat dissipation to one shell.
  • the shells adhering to the rollers 3, 4 are conveyed into the casting area 5 by the rotation of the rollers 3, 4, where they are pressed together under the effect of a band forming force K to form the cast strip B.
  • the effective cooling in the casting area 5 and the band forming force K are coordinated so that the continuously emerging from the casting area 5 cast strip B is largely completely solidified.
  • the cast strip B In order to suppress crystallization effects, the cast strip B, following the casting area 5, enters a cooling device 7, which applies a cooling medium to the cast strip B, so that it cools further.
  • the cooling by the cooling device 7 sets in the immediate connection to the casting area 5 and takes place so strong that the temperature T of cast strip B decreases steadily until it is below the glass transition temperature T G of each cast melt S. Any crystallization of the structure of the cast strip B is thus suppressed, so that it is still in an amorphous state on reaching the conveying path 6.
  • the emerging from the casting area 5 Band B is initially conveyed away vertically in the direction of gravity R and then deflected in a known manner in a continuously curved arc in a horizontally oriented conveying path 6.
  • the cast strip B can then pass through a heating device 8 in which the strip B is through- heated at an annealing temperature T annealing above the crystallization temperature Tx of the respectively cast molten steel S over an annealing time t ann .
  • the aim of this heat treatment is the controlled formation of a fine crystalline microstructure with grain sizes ranging from 10 to 10,000 nm in the cast strip B.
  • the cast strip B thus heat treated is then hot rolled in a hot rolling mill 9 to hot strip WB.
  • a cast strip B has been produced in each case from three steel melts S with the compositions Z1, Z2, Z3 given in Table 1.
  • the thickness D of the tapes B cast from the respective molten steel S the cooling rate AR achieved in each case during the cooling of the melt S in the casting region 5, which in each case during the cooling of the from the casting area 5 emerging cast bands B scored in the additional cooling device 7 cooling rate ARZ and the target temperature T z of the additional cooling specified.
  • Table 2 shows the microstructural state and any structural constituents of the resulting band.
  • the cast strip B before the heat treatment already had a fine crystalline structure of ⁇ -Fe, Fe 2 B, Fe 3 B and Fe 3 Si at a hardness of HV0.5 of 840-900. Even after the heat treatment, the microstructure consisted of ⁇ -Fe, Fe 2 B, Fe 3 B and Fe 3 Si, but the hardness was now HV0.5 760-810.
  • the invention thus provides methods for producing a steel strip B having an amorphous, partially amorphous or fine-crystalline structure with grain sizes in the range from 10 to 10,000 nm and a correspondingly obtained flat steel product.
  • a molten steel in a casting device (2) cast into a cast strip (B) and cooled accelerated.
  • the melt contains at least two further elements which belong to the group "Si, B, C, P".
  • Si, B, C, P the contents of these elements (in% by weight) Si: 1.2 to 7.0%, B: 0.4 to 4.0%, C: 0.5 to 4.0% , P: 1.5-8.0%.
  • the molten steel containing Si, B, C and P is formed in a casting device (2) whose casting region (5) is formed on at least one of its longitudinal sides by a wall which moves and cools in the casting direction (G) during the casting operation. to a cast strip (B), wherein the molten steel (S) is cooled by contact with the moving cooled wall at a cooling rate of at least 200 K / sec.

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Claims (15)

  1. Procédé de production d'un produit plat en acier avec une structure amorphe, partiellement amorphe ou cristalline fine, où la structure cristalline fine présente des tailles de grains dans le domaine allant de 10 à 10 000 nm, lors duquel de l'acier en fusion est coulé en une bande coulée (B) dans un dispositif de coulée (2), et est refroidi de manière accélérée, où l'acier en fusion contient, outre du fer et des impuretés inévitables inhérentes à la production, au moins deux autres éléments faisant partie du groupe « Si, B, C, P » avec la teneur (en % en poids) :
    Si : 1,2 - 7,0 %,
    B : 0,4 - 4,0 %,
    C : 0,5 - 4,0 %,
    P : 1,5 - 8,0 %
    ainsi qu'optionnellement un ou plusieurs des éléments du groupe « Cu, Cr, Al, N, Nb, Mn, Ti, V » avec les teneurs (en % en poids) :
    Cu : jusqu'à 5,0 %,
    Cr : jusqu'à 10,0 %,
    Al : jusqu'à 10,0 %,
    N : jusqu'à 0, 5 %,
    Nb : jusqu'à 2,0 %,
    Mn : jusqu'à 3,0 %,
    Ti : jusqu'à 2,0 %,
    V : jusqu'à 2,0 %,
    caractérisé en ce que
    le dispositif de coulée (2) présente une zone de coulée (5) dans laquelle la bande coulée (B) est formée, cette zone de coulée (5) étant formée sur au moins un de ses côtés longitudinaux par une paroi qui refroidit et se meut pendant l'opération de coulée, cette paroi étant formée par deux rouleaux de coulée en rotation inverse (3, 4) ou par une bande qui se meut dans la direction de coulée (G)pendant l'opération de coulée, , et en ce que la bande coulée (B) présente une épaisseur de 0,8 - 4,5 mm.
  2. Procédé selon la revendication 1, caractérisé en ce que l'acier en fusion est refroidi avec une vitesse de refroidissement d'au moins 200 K/s jusqu'à en-deçà de la température de transition vitreuse TG.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que la bande coulée (B) amorphe ou partiellement amorphe est laminée à chaud à une température initiale de laminage à chaud se situant dans une plage entre la température de transition vitreuse et la température de cristallisation Tx pour créer le feuillard chaud.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'acier en fusion (S) est refroidi par contact avec la paroi refroidie en mouvement avec une vitesse de refroidissement d'au moins 200 K/s.
  5. Procédé selon la revendication 4, caractérisé en ce que le refroidissement de la bande coulée (B) est poursuivi après la sortie de la zone de coulée (5) avec une vitesse de refroidissement d'au moins 200 K/s.
  6. Procédé selon l'une des revendications 4 ou 5, caractérisé en ce que la bande coulée (B) sortant de la zone de coulée (5) est refroidie en continu jusqu'à dépasser vers le bas la température de transition vitreuse TG de l'acier respectif.
  7. Procédé selon l'une des revendications 4 à 6, caractérisé en ce que la bande coulée (B) est laminée à chaud à une température initiale de laminage à chaud étant de 500 - 1 000 °C pour créer un feuillard chaud.
  8. Procédé selon l'une des revendications 4 à 7, caractérisé en ce que la bande coulée (B) sortant de la zone de coulée (5) du dispositif de coulée (2) et étant optionnellement additionnellement refroidie, présente une structure amorphe ou partiellement amorphe et en en ce que la bande coulée (B) ainsi obtenue est recuite à une température de recuit TGlüh correspondant à au moins la température de cristallisation Tx de l'acier respectif.
  9. Procédé selon la revendication 8, caractérisé en ce que la température de recuit TGlüh se situe dans une plage entre 500 et 1 000 °C.
  10. Procédé selon l'une des revendications 4 à 9, caractérisé en ce que l'acier en fusion (S) contient, outre les au moins deux éléments du groupe Si, B, C et P, au moins un élément du groupe Cu, Cr, Al, N, Nb, Mn, Ti et V.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le dispositif de coulée (2) est un dispositif de coulée à deux rouleaux, dont les rouleaux (3, 4) contrarotatifs autour d'axes (X1, X2) orientés parallèlement l'un par rapport à l'autre forment, respectivement, une paroi longitudinale refroidie de la zone de coulée (5) avançant, lors de l'opération de coulée, en continu dans la direction de coulée (G) dans laquelle la bande (B) est formée.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce qu'une des teneurs suivantes s'applique respectivement à au moins un des éléments du groupe « Si, B, C, P » (en % en poids) :
    Si : 2,0 - 6,0 %,
    B : 0,4 - 3,0 %,
    C : 0,5 - 3,0 %
    ou
    P : 2,0 - 6,0 %.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'acier en fusion contient, respectivement optionnellement, (en % en poids) au moins 0,1 % de Cu, au moins 0,5 % de Cr, au moins 1,0 % d'Al et au moins 0,005 % de N.
  14. Produit plat en acier constitué d'un acier qui contient, outre du fer et des impuretés inévitables inhérentes à la production, au moins deux autres éléments du groupe Si, B, C et P avec la teneur (en % en poids) :
    Si : 1,2 - 7,0 %,
    B : 0,4 - 4,0 %,
    C : 0,5 - 4,0 %,
    P : 1,5 - 8,0 %,
    ainsi qu'optionnellement un ou plusieurs éléments du groupe « Cu, Cr, Al, N, Nb, Mn, Ti, V » avec la teneur (en % en poids) :
    Cu : jusqu'à 5,0 %,
    Cr : jusqu'à 10,0 %
    Al : jusqu'à 10,0 %
    N : jusqu'à 0,5 %,
    Nb : jusqu'à 2,0 %,
    Mn : jusqu'à 3,0 %,
    Ti : jusqu'à 2,0 %,
    V : jusqu'à 2,0 %,
    le produit plat en acier présentant une structure amorphe, partiellement amorphe ou cristalline fine avec des tailles de grains dans le domaine allant de 10 à 10 000 nm, caractérisé en ce que le produit plat enacier présente une épaisseur entre 0,8 et 4,5 mm.
  15. Produit plat en acier selon la revendication 14, caractérisé en ce qu'une des teneurs suivantes (en % en poids) s'applique respectivement à au moins un des éléments du groupe « Si, B, C, P » :
    Si : 2,0 - 6,0 %,
    B : 0,4 - 3,0 %,
    C : 0,5 - 3,0 %,
    ou
    P : 2,0 - 6,0 %.
EP13152793.9A 2013-01-25 2013-01-25 Procédé destiné à générer un produit plat en acier avec une structure cristalline fine, partiellement amorphe ou amorphe et produit plat en acier conçu de la sorte Not-in-force EP2759614B1 (fr)

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EP13152793.9A EP2759614B1 (fr) 2013-01-25 2013-01-25 Procédé destiné à générer un produit plat en acier avec une structure cristalline fine, partiellement amorphe ou amorphe et produit plat en acier conçu de la sorte
EP14701377.5A EP2948572A1 (fr) 2013-01-25 2014-01-24 Procédé de production d'un produit en tôle d'acier doté d'une structure amorphe, partiellement amorphe ou microcristalline et produit en tôle d'acier ainsi obtenu
JP2015554158A JP6457951B2 (ja) 2013-01-25 2014-01-24 アモルファス微細構造、部分的アモルファス微細構造又は微結晶微細構造を備えた平鋼製品を製造するための方法及びこのような特性を備えた平鋼製品
PCT/EP2014/051416 WO2014114756A1 (fr) 2013-01-25 2014-01-24 Procédé de production d'un produit en tôle d'acier doté d'une structure amorphe, partiellement amorphe ou microcristalline et produit en tôle d'acier ainsi obtenu
KR1020157022868A KR102203018B1 (ko) 2013-01-25 2014-01-24 무정형, 부분 무정형, 또는 미세 결정형 조직을 보유하는 평강 제품의 제조 방법, 및 상응하는 유형의 평강 제품
US14/763,249 US10730105B2 (en) 2013-01-25 2014-01-24 Method for producing a flat steel product with an amorphous, partially amorphous or fine-crystalline microstructure and flat steel product with such characteristics
CN201480018468.1A CN105143491B (zh) 2013-01-25 2014-01-24 制造具有非晶态、部分非晶态或细晶微结构的扁钢产品的方法及具有此特性的扁钢产品
BR112015017627-5A BR112015017627B1 (pt) 2013-01-25 2014-01-24 Método de produção de um produto de aço plano com uma microestrutura amorfa, parcialmente amorfa ou cristalina fina e produto de aço plano com tais características

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KR102203018B1 (ko) 2021-01-14
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