EP2759614B1 - Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt - Google Patents

Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt Download PDF

Info

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
Authority
EP
European Patent Office
Prior art keywords
casting
amorphous
strip
cooled
cast strip
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13152793.9A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2759614A1 (de
Inventor
Dorothée DORNER
Christian Höckling
Harald Hofmann
Matthias Schirmer
Markus DAAMEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Steel Europe AG
Original Assignee
ThyssenKrupp Steel Europe AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP13152793.9A priority Critical patent/EP2759614B1/de
Application filed by ThyssenKrupp Steel Europe AG filed Critical ThyssenKrupp Steel Europe AG
Priority to PCT/EP2014/051416 priority patent/WO2014114756A1/de
Priority to US14/763,249 priority patent/US10730105B2/en
Priority to EP14701377.5A priority patent/EP2948572A1/de
Priority to CN201480018468.1A priority patent/CN105143491B/zh
Priority to KR1020157022868A priority patent/KR102203018B1/ko
Priority to JP2015554158A priority patent/JP6457951B2/ja
Priority to BR112015017627-5A priority patent/BR112015017627B1/pt
Publication of EP2759614A1 publication Critical patent/EP2759614A1/de
Application granted granted Critical
Publication of EP2759614B1 publication Critical patent/EP2759614B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00Special casting characterised by the nature of the product
    • B22D25/06Special casting characterised by the nature of the product by its physical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0611Continuous 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622Continuous 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/002Heat treatment of ferrous alloys containing Cr
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/005Heat treatment of ferrous alloys containing Mn
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/008Heat treatment of ferrous alloys containing Si
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/11Making amorphous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/003Making ferrous alloys making amorphous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20Ferrous alloys, e.g. steel alloys containing chromium with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32Ferrous alloys, e.g. steel alloys containing chromium with boron
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/02Amorphous alloys with iron as the major constituent
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2201/00Treatment for obtaining particular effects
    • C21D2201/03Amorphous 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Continuous Casting (AREA)
  • Metal Rolling (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)
EP13152793.9A 2013-01-25 2013-01-25 Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt Not-in-force EP2759614B1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP13152793.9A EP2759614B1 (de) 2013-01-25 2013-01-25 Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt
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
EP14701377.5A EP2948572A1 (de) 2013-01-25 2014-01-24 Verfahren zum erzeugen eines stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen gefüge und derart beschaffenes stahlflachprodukt
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
PCT/EP2014/051416 WO2014114756A1 (de) 2013-01-25 2014-01-24 Verfahren zum erzeugen eines stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen gefüge und derart beschaffenes stahlflachprodukt
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
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
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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP13152793.9A EP2759614B1 (de) 2013-01-25 2013-01-25 Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt

Publications (2)

Publication Number Publication Date
EP2759614A1 EP2759614A1 (de) 2014-07-30
EP2759614B1 true EP2759614B1 (de) 2019-01-02

Family

ID=47681703

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13152793.9A Not-in-force EP2759614B1 (de) 2013-01-25 2013-01-25 Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt
EP14701377.5A Withdrawn EP2948572A1 (de) 2013-01-25 2014-01-24 Verfahren zum erzeugen eines stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen gefüge und derart beschaffenes stahlflachprodukt

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP14701377.5A Withdrawn EP2948572A1 (de) 2013-01-25 2014-01-24 Verfahren zum erzeugen eines stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen gefüge und derart beschaffenes stahlflachprodukt

Country Status (7)

Country Link
US (1) US10730105B2 (ko)
EP (2) EP2759614B1 (ko)
JP (1) JP6457951B2 (ko)
KR (1) KR102203018B1 (ko)
CN (1) CN105143491B (ko)
BR (1) BR112015017627B1 (ko)
WO (1) WO2014114756A1 (ko)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3425082B1 (en) 2013-08-28 2024-05-15 Innovex Downhole Solutions Inc. Chromium-free thermal spray composition, method, and apparatus
CN104593701B (zh) * 2015-01-15 2017-01-04 江苏本安环保科技有限公司 一种铁基非晶合金阻隔防爆材料
DE102015217627B4 (de) 2015-09-15 2017-07-20 Thyssenkrupp Ag Bandbearbeitungsvorrichtung sowie Verfahren zur Bearbeitung eines Bands
DE102015116517A1 (de) 2015-09-29 2017-03-30 Thyssenkrupp Ag Vorrichtung und Verfahren zur kontinuierlichen Herstellung eines bandförmigen, metallischen Werkstücks
CN105838993B (zh) 2016-04-05 2018-03-30 宝山钢铁股份有限公司 具有增强弹性模量特征的轻质钢、钢板及其制造方法
US11655519B2 (en) 2017-02-27 2023-05-23 Nucor Corporation Thermal cycling for austenite grain refinement
CN112585287B (zh) * 2018-08-28 2022-03-01 杰富意钢铁株式会社 热轧钢板、冷轧钢板及它们的制造方法
CN109457168B (zh) * 2018-12-24 2021-07-06 宁波正直科技有限公司 家用燃气灶燃气管合金及其制备方法和燃气管
CN109719264B (zh) * 2019-02-26 2020-10-02 安徽智磁新材料科技有限公司 一种防锈非晶合金及其制备方法
CN109957732B (zh) * 2019-04-08 2020-11-27 东北大学 一种锆基非晶薄带材连续制备的方法
CN109825781B (zh) * 2019-04-08 2021-02-05 东北大学 一种铁基非晶薄带材连续制备的方法
CN109967703B (zh) * 2019-04-08 2020-09-18 东北大学 一种厚度为80~1500μm的宽幅非晶薄带连续大冷速高效制备的方法
CN109822067B (zh) * 2019-04-08 2020-12-18 东北大学 一种镍基非晶薄带材连续制备的方法
CN110195187B (zh) * 2019-05-17 2020-06-05 北京科技大学 一种高弹性模量汽车用钢铁材料及其制备方法
DE102019004114A1 (de) * 2019-06-08 2020-06-18 Daimler Ag Stahllegierung, Bauteil, insbesondere für ein Kraftfahrzeug, sowie Verfahren zum Herstellen eines solchen Bauteils
DE102019122515A1 (de) * 2019-08-21 2021-02-25 Ilsenburger Grobblech Gmbh Verfahren zur Herstellung von hochfesten Blechen oder Bändern aus einem niedrig legierten, hochfesten bainitischen Stahl sowie ein Stahlband oder Stahlblech hieraus
DE102021116380B4 (de) 2021-06-24 2023-04-06 Thyssenkrupp Steel Europe Ag Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen oder teilamorphen Gefüge und Produkt hergestellt aus einem solchen Stahlflachprodukt

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE789989A (ko) 1971-10-15 1973-02-01 Arbed
US4219355A (en) * 1979-05-25 1980-08-26 Allied Chemical Corporation Iron-metalloid amorphous alloys for electromagnetic devices
JPS57193005A (en) * 1981-05-23 1982-11-27 Tdk Corp Amorphous magnetic alloy thin belt for choke coil and magnetic core for the same
JPS5964143A (ja) 1982-10-04 1984-04-12 Nippon Steel Corp 鉄心用非晶質合金薄帯の製造方法
JPS6376842A (ja) 1986-09-18 1988-04-07 Kawasaki Steel Corp トランス鉄心用非晶質合金薄帯の製造方法
JPH04266460A (ja) 1991-02-19 1992-09-22 Nippon Steel Corp 双ロール式薄板連続鋳造における2次冷却方法
JPH0559483A (ja) 1991-08-30 1993-03-09 Kawasaki Steel Corp 商用周波数帯トランス用非晶質合金薄帯の製造方法
JPH05291019A (ja) 1992-04-13 1993-11-05 Nippon Steel Corp Fe基非晶質合金の製造方法
JPH06274050A (ja) 1993-03-23 1994-09-30 Tokyo Electric Co Ltd 転写装置
JPH06297109A (ja) 1993-04-15 1994-10-25 Nippon Steel Corp 表面性状の優れたCr−Ni系ステンレス鋼薄肉鋳片の製造方法
US5958153A (en) * 1995-04-11 1999-09-28 Nippon Steel Corporation Fe-system amorphous metal alloy strip having enhanced AC magnetic properties and method for making the same
JPH08283919A (ja) 1995-04-11 1996-10-29 Nippon Steel Corp Fe基非晶質合金薄帯およびその製造方法
JP3634286B2 (ja) 2000-11-27 2005-03-30 新日本製鐵株式会社 Fe基非晶質合金薄帯とそれを用いて製造した鉄心
US6416879B1 (en) * 2000-11-27 2002-07-09 Nippon Steel Corporation Fe-based amorphous alloy thin strip and core produced using the same
JP3929327B2 (ja) 2002-03-01 2007-06-13 独立行政法人科学技術振興機構 軟磁性金属ガラス合金
WO2003085150A1 (en) * 2002-04-05 2003-10-16 Nippon Steel Corporation Fe-BASE AMORPHOUS ALLOY THIN STRIP OF EXCELLENT SOFT MAGNETIC CHARACTERISTIC, IRON CORE PRODUCED THEREFROM AND MASTER ALLOY FOR QUENCH SOLIDIFICATION THIN STRIP PRODUCTION FOR USE THEREIN
EP1545814B1 (en) 2002-09-27 2012-09-12 Postech Foundation Method and apparatus for producing amorphous alloy sheet, and amorphous alloy sheet produced using the same
CN101027148A (zh) * 2004-04-28 2007-08-29 纳米钢公司 纳米晶体薄钢板
JP4849545B2 (ja) 2006-02-02 2012-01-11 Necトーキン株式会社 非晶質軟磁性合金、非晶質軟磁性合金部材、非晶質軟磁性合金薄帯、非晶質軟磁性合金粉末、及びそれを用いた磁芯ならびにインダクタンス部品
JP5057551B2 (ja) 2006-06-21 2012-10-24 株式会社神戸製鋼所 Zr基金属ガラス板材
JP4319206B2 (ja) 2006-07-20 2009-08-26 独立行政法人科学技術振興機構 軟磁性Fe基金属ガラス合金
US8133333B2 (en) * 2006-10-18 2012-03-13 The Nanosteel Company, Inc. Processing method for the production of nanoscale/near nanoscale steel sheet
ES2325962T3 (es) 2006-10-30 2009-09-25 Thyssenkrupp Steel Ag Procedimiento para fabricar productos planos de acero a partir de un acero multifasico microaleado con boro.
CN101595237B (zh) * 2006-12-04 2011-12-14 东北泰克诺亚奇股份有限公司 非晶态合金组合物
KR101354935B1 (ko) 2006-12-20 2014-01-27 재단법인 포항산업과학연구원 스트립 캐스팅에 의한 비정질 스트립 제조시 냉각장치
EP2163659B1 (de) 2008-09-11 2016-06-08 Outokumpu Nirosta GmbH Nichtrostender Stahl, aus diesem Stahl hergestelltes Kaltband und Verfahren zur Herstellung eines Stahlflachprodukts aus diesem Stahl
DE102009048165A1 (de) 2009-10-02 2011-04-07 Sms Siemag Ag Verfahren zum Bandgießen von Stahl und Anlage zum Bandgießen
DE102011000089A1 (de) 2011-01-11 2012-07-12 Thyssenkrupp Steel Europe Ag Verfahren zum Herstellen eines warmgewalzten Stahlflachprodukts
CN102605293A (zh) 2012-04-18 2012-07-25 江苏省沙钢钢铁研究院有限公司 低温韧性优异的非调质低裂纹敏感性钢板及其生产方法
CN102796969B (zh) 2012-08-31 2015-08-26 宝山钢铁股份有限公司 一种含硼微合金耐大气腐蚀钢及其制造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
KR102203018B1 (ko) 2021-01-14
US20150360285A1 (en) 2015-12-17
EP2759614A1 (de) 2014-07-30
EP2948572A1 (de) 2015-12-02
BR112015017627A2 (pt) 2017-07-11
US10730105B2 (en) 2020-08-04
BR112015017627B1 (pt) 2020-09-15
WO2014114756A1 (de) 2014-07-31
CN105143491B (zh) 2016-12-14
JP6457951B2 (ja) 2019-01-23
CN105143491A (zh) 2015-12-09
KR20150110729A (ko) 2015-10-02
JP2016507383A (ja) 2016-03-10

Similar Documents

Publication Publication Date Title
EP2759614B1 (de) Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen, teilamorphen oder feinkristallinen Gefüge und derart beschaffenes Stahlflachprodukt
DE60014145T2 (de) Verfahren zum herstellen von kohlenstoffstahlbändern, insbesondere für verpackungsmaterial, und so hergestellte bändern
DE69208528T2 (de) Verfahren zur Formgebung von amorphen metallischen Werkstoffen
EP1752548B1 (de) Verfahren zur Herstellung von kornorientiertem Elektroband
EP2761041B1 (de) Verfahren zum herstellen eines kornorientierten, für elektrotechnische anwendungen bestimmten elektrobands oder -blechs
DE60219484T2 (de) Verfahren zum bearbeiten stranggegossenen metallischen brammen oder bändern
DE69628312T2 (de) Verfahren zur herstellung von getraenkedosenblech
EP3019292B1 (de) Verfahren zur erzeugung eines flachproduktes aus einer eisenbasierten formgedächtnislegierung
EP2729588B1 (de) Verfahren zum herstellen eines kornorientierten, für elektrotechnische anwendungen bestimmten elektrostahlflachprodukts
DE112013001191B4 (de) Verfahren zum Herstellen eines Bandes aus amorpher Legierung
DE102012002642B4 (de) Warmband zur Herstellung eines Elektroblechs und Verfahren hierzu
EP1319091B1 (de) Verfahren zum herstellen eines überwiegend aus mn-austenit bestehenden stahlbands oder -blechs
DE112013001401T5 (de) Band aus amorpher legierung
EP1341937B1 (de) Verfahren zum erzeugen eines warmbandes aus einem einen hohen mangan-gehalt aufweisenden stahl
DE102009018683A1 (de) Verfahren und Vorrichtung zum Stranggießen einer Bramme
DE102009036378A1 (de) Verfahren und Vorrichtung zum Herstellen eines mikrolegierten Stahls, insbesondere eines Röhrenstahls
DE112015005690T5 (de) Warmgewalztes martensitisches Leichtbau-Stahlblech und Verfahren zum Herstellen desselben
DE69621351T2 (de) Giessbänder zum giessen von metallen, verfahren zu deren herstellung und verwendung derselben
DE102014005662A1 (de) Werkstoffkonzept für einen umformbaren Leichtbaustahl
EP2483014B1 (de) Verfahren zum bandgiessen von stahl und anlage zum bandgiessen
EP1802405B1 (de) Verfahren zum herstellen von blechen aus einer magnesiumschmelze
EP2756897A1 (de) Verfahren zum Herstellen eines als metallischer Verbundwerkstoff ausgeführten Flachprodukts
EP1228255A1 (de) Verfahren zum herstellen eines warmbandes
DE102021116380B4 (de) Verfahren zum Erzeugen eines Stahlflachprodukts mit einem amorphen oder teilamorphen Gefüge und Produkt hergestellt aus einem solchen Stahlflachprodukt
DE102012108648B4 (de) Verfahren zur Herstellung eines Bauteils aus einem Gießband aus einer Magnesiumlegierung mit gutem Umformverhalten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130125

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

R17P Request for examination filed (corrected)

Effective date: 20150130

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20160226

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180711

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1084471

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013011941

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20190102

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190502

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190402

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190403

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190402

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190502

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190125

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013011941

Country of ref document: DE

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190131

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

26N No opposition filed

Effective date: 20191003

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20190402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190125

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20210118

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210119

Year of fee payment: 9

Ref country code: AT

Payment date: 20210119

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190102

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502013011941

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1084471

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220802

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220131